EP1674497A1 - Use of polyarylene ether ketone powder in a powder-based tridimensional tool-less method of manufacturing and shaped articles obtained therefrom - Google Patents
Use of polyarylene ether ketone powder in a powder-based tridimensional tool-less method of manufacturing and shaped articles obtained therefrom Download PDFInfo
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- EP1674497A1 EP1674497A1 EP05110112A EP05110112A EP1674497A1 EP 1674497 A1 EP1674497 A1 EP 1674497A1 EP 05110112 A EP05110112 A EP 05110112A EP 05110112 A EP05110112 A EP 05110112A EP 1674497 A1 EP1674497 A1 EP 1674497A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/141—Processes of additive manufacturing using only solid materials
- B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G6/00—Condensation polymers of aldehydes or ketones only
- C08G6/02—Condensation polymers of aldehydes or ketones only of aldehydes with ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the invention relates to the use of a porous polyarylene ether ketone (PAEK) having a BET surface area between 1 and 60 m 2 / g, preferably between 5 and 45 m 2 / g, particularly preferably between 15 and 40 m 2 / g, that to a powder as well as modifications of this powder, the use thereof in a layer-by-layer process with which selectively areas of a powdery layer are melted by introduction of electromagnetic energy, and moldings produced by a method mentioned above.
- PEEK porous polyarylene ether ketone
- the porous PAEK is usually prepared by reacting an aromatic dihalogen compound with a bisphenol and / or a halophenol in the presence of alkali or alkaline earth carbonate or bicarbonate in a high boiling aprotic solvent to a PAEK, discharging and solidifying the melt, optionally grinding, z , In a hammer mill, extracting the resulting particles with one or more organic solvents to remove the reaction solvent and with water to remove the inorganic salts, and then drying.
- the particles to be extracted may be prepared from the reaction mixture other than by milling, also by granulating an extruded strand, applying a drop to a chilled metal strip, prilling or spray-drying.
- the degree of porosity obtained after the extraction depends in particular on the content of reaction solvent in the material to be extracted. In this respect, it is advantageous to remove only a portion of the reaction solvent during spray drying. Otherwise, the way in which the particles to be extracted are produced is not critical.
- a PAEK which was possibly produced by a different process and which is in a compact form, for.
- granules are dissolved in a suitable high-boiling aprotic solvent, whereupon the hot solution, as described above for the melt obtained in the reaction, converted into particle form and extracted with one or more organic solvents.
- the high-boiling aprotic solvent is preferably a compound of the formula according to the prior art wherein T represents a direct bond, an oxygen atom or two hydrogen atoms; Z and Z 'are hydrogen or phenyl groups. This is preferably diphenylsulfone.
- the PAEK contains units of the formulas (-Ar-X-) and (-Ar'-Y-), wherein Ar and Ar 'represent a bivalent aromatic radical, preferably 1,4-phenylene, 4,4'-biphenylene and 1,4- 1,5- or 2,6-naphthylene.
- X is an electron-withdrawing group, preferably carbonyl or sulfonyl, while Y represents a group such as O, S, CH 2 , isopropylidene or the like. This should be at least 50%, preferably at least 70% and especially preferably at least 80% of the groups X represent a carbonyl group, while at least 50%, preferably at least 70% and particularly preferably at least 80% of the groups Y should consist of oxygen.
- the PAEK may be, for example, a polyetheretherketone (PEEK; Formula I), a polyetherketone (PEK; Formula II), a polyetherketone ketone (PEKK; Formula III), or a polyetheretherketone ketone (PEEKK; Formula IV), but of course other arrangements are contemplated the carbonyl and oxygen groups possible.
- the PAEK is generally semicrystalline, as evidenced, for example, in the DSC analysis by finding a crystalline melting point T m , which is of the order of magnitude of 300 ° C or higher in most cases.
- T m crystalline melting point
- the teaching of the invention is also applicable to amorphous PAEK.
- sulfonyl groups, biphenylene groups, naphthylene groups or bulky groups Y such as.
- As an isopropylidene group reduce the crystallinity.
- the viscosity number measured according to DIN EN ISO 307 on a solution of 250 mg PAEK in 50 ml of 96 weight percent H 2 SO 4 at 25 ° C, about 20 to 150 cm 3 / g and preferably 50 to 120 cm 3 / g.
- the BET surface area is determined according to DIN ISO 66131.
- the porous PAEK may be milled at room temperature or elevated temperature, but to improve milling and milling yield it is advantageous to grind at a lower temperature, preferably below 0 ° C, more preferably below -20 ° C, and most preferably below -40 ° C.
- a lower temperature preferably below 0 ° C, more preferably below -20 ° C, and most preferably below -40 ° C.
- pin mill, fluidized bed opposed jet mills or baffle mills are suitable.
- the porous structure of the PAEK to be grounded provides weak points which lead to breakage under the abovementioned conditions.
- the regrind can be subsequently screened or sieved.
- a finely powdered PAEK which can be used for the process according to the invention can be produced with a number-average particle diameter (d 50 ) of 30 to 150 ⁇ m, preferably 45 to 120 ⁇ m, particularly preferably 48 to 100 ⁇ m.
- the determination of the particle diameter and its distribution is carried out by laser diffraction according to DIN ISO 13320-1.
- processes are particularly suitable which work on the basis of pulverulent thermoplastic materials and in which the desired structures are produced in layers by selective melting and solidification.
- On support structures for overhangs and undercuts can be dispensed with, since the powder bed surrounding the molten areas provides sufficient support effect. It also eliminates the rework to remove columns.
- the methods are also suitable for the production of small batches.
- the invention relates to a process for using a powder based on PAEK and molded articles, produced by a layer-by-layer process, with which selectively areas of a layer are melted by applying electromagnetic energy, using this powder.
- the melted areas solidify on cooling, thereby forming the desired shaped body. Excess powder material is removed.
- One method which is particularly well suited for the purpose of rapid prototyping or rapid manufacturing is laser sintering.
- plastic powders in a chamber are selectively exposed briefly to a laser beam, thereby melting the powder particles that are hit by the laser beam.
- the molten particles run into each other and solidify after cooling back to a solid mass.
- the selectivity of the layered processes can be done via the application of susceptors, absorbers, inhibitors, or by masks, or via focused energy input, such as by a laser beam or by a fiber optic cable.
- the laser sintering process produces a block-like body, which consists of the desired components on the one hand and, for the most part, predominantly unexposed powder, so-called powdered powder, which remains in this block until demoulding or unpacking with the components. It has a supporting effect on the components, so that overhangs and undercuts can be realized with the laser sintering process without supporting structures.
- the unexposed powder can be used in a further building process after sieving and addition of new powder (recycling).
- a disadvantage of the prior art is that a highly heat-resistant material for use in a three-dimensional process in which layered powdered material is selectively melted by means of electromagnetic waves and forms the desired three-dimensional structure after cooling, has not been commercially available.
- the reason lies firstly in the difficulty of producing a sufficiently fine powder.
- Sufficiently fine means that the desired degree of dissolution of the components is achieved, and at the same time the layer thickness is low enough that the selectively introduced energy is sufficient to ensure the melting of a layer.
- the average grain diameter of a powder for use in any of the described methods the range of 30 to 150 ⁇ m may be cited. Yields in the milling of less than 10% are generally not regarded as a commercially usable solution.
- the temperatures at which especially the high-temperature-deforming materials are processed are very high and are therefore difficult or even impossible to process in the rapid prototyping / rapid-manufacturing machines on the market.
- the cause is also in the very low BET surface areas of a PAEK powder according to the prior art, which lead to a deteriorated energy absorption of the particle to be melted.
- a powder as described above, can be used as a base material for use in the described three-dimensional process.
- the parts produced with this powder have a higher mechanical strength and higher heat distortion resistance than components from, for example, the currently available standard material EOSINT P2200 (supplier EOS GmbH, Krailling, Germany) or Duraform (provider 3D-Systems, Valencia, California) for laser sintering.
- the material is optimized with respect to the grain distribution and used equipped with a Riesel faux generate according to the prior art.
- a subsequent rounding of the sharp-edged by the grinding process particles by mechanical action, for example in a high-speed mixer may be advantageous.
- Particular preference is given to equipping the powder regions to be melted with an IR absorber, which may already be present in the powder, for example, or during processing by application of the absorber to the areas to be melted by inkjet method or scattering or spraying method.
- Base material is a grinding powder based on PAEK (polyarylene ether ketone). It is characterized by the milling of PAEK particles having a BET surface area of at least 1 m 2 / g. This may preferably be PEEK, PEK, PEKK, or PEEKK.
- the average particle diameter d50 for use in a three-dimensional process is between 30 and 150 .mu.m, preferably between 45 and 120 .mu.m , and most preferably between 48 and 100 microns.
- the proportion of particles smaller than 30 .mu.m can be reduced, for example by sifting. It may also be useful to remove particles which are larger or only slightly smaller than the layer thickness set in the process, for example by means of sieving.
- the particle size distribution of the powder according to the invention used in the RP / RM process can be narrow, broad or even bimodal.
- the PAEK powder which serves as a basis for the present invention has a BET surface area between 1 m 2 / g and 60 m 2 / g, preferably between 5 m 2 / g and 45 m 2 / g, and more preferably between 15 m 2 / g and 40 m 2 / g.
- the large surface leads to a better and more uniform absorption of the electromagnetic energy, which is used for selective melting of areas of a powder layer is needed.
- the crystallite melting point of the powder of the invention depends on the type of PAEK used; it is above 300 ° C.
- the preferred range for solution viscosity is between 0.2 and 1.3, more preferably between 0.5 and 1.1.
- the solution viscosity at the PAEK is determined in accordance with EN ISO 1628-1 or in accordance with DIN EN ISO 307 in 96% sulfuric acid.
- a further advantageous modification of the PAEK powder is the incorporation of a suitable absorber.
- the absorber can either be evenly distributed in the particle, in the Focus inside or near the surface.
- the absorber may be colorants or other additives.
- examples thereof are carbon black, KHP (copper hydroxide phosphate), bone char, flame retardants based on melamine cyanurate or phosphorus, carbon fibers, chalk, graphite or for predominantly transparent powders, for example interference pigments and ClearWeld® (WO 0238677), without wishing to restrict the invention to this.
- the modification of the PAEK powder can be done in a variety of ways. Therefore, the present invention is also a process for the modification of PAEK powder, which is characterized in that either a powdered mixture of the PAEK powder according to the invention and a corresponding absorber is prepared.
- the powder according to the invention has, based on the sum of the polymers present in the powder, preferably from 0.01 to 30% by mass of an absorber, preferably from 0.05 to 20% by mass of an absorber, particularly preferably from 0.2 to 15% by mass. % of an absorber and most preferably from 0.4 to 10% by mass of an absorber.
- the ranges given here are based on the total content of an excitable by electromagnetic energy absorber in the powder, wherein powder is meant the entire amount consisting of components.
- the powder according to the invention may comprise a mixture of an absorber and polymer particles or else polymer particles or powder having incorporated absorbers.
- the absorber preferably has a particle size which the average particle size d 50 of the polymer particles or powder by at least 20%, preferably by more than 50% and completely more preferably below by more than 70%.
- the absorber has an average particle size of 0.001 to 50 microns, preferably from 0.02 to 10 microns. Due to the small particle size, there is a good distribution of the powdered absorber in the powdery polymer powder.
- the absorber has a so-called colorant.
- a colorant is understood to mean all colorants according to DIN 55944, which can be classified into inorganic and organic colorants and into natural and synthetic colorants (see Rompps Chemie Lexikon, 1981, 8th edition, page 1237).
- DIN 55943 Sept. 1984
- DIN 55945 Advantix
- a pigment is a virtually insoluble, inorganic or organic, colored or achromatic colorant in the application medium.
- Dyes are soluble in solvents and / or binders inorganic or organic, colored or achromatic colorants.
- the absorber can also receive its absorbing effect by having additives.
- melamine cyanurate-based flame retardants can be, for example, melamine cyanurate-based flame retardants (Melapur from the DSM) or based on phosphorus, preferably phosphates, phosphites, phosphonites, or elemental red phosphorus.
- phosphorus preferably phosphates, phosphites, phosphonites, or elemental red phosphorus.
- carbon fibers preferably ground, glass beads, also hollow, or kaolin, chalk, wollastonite, or graphite.
- the absorber contained in the powder according to the invention preferably has carbon black or KHP (Kupferhydroxidphoshat) or chalk, bone charcoal, carbon fibers, graphite, flame retardants or interference pigments as the main component.
- Interference pigments are so-called pearlescent pigments. Based on the natural mineral mica, they are coated with a thin layer of metal oxides, for example titanium dioxide and / or iron oxide, and are available with a mean particle size distribution between 1 and 60 ⁇ m. Interference pigments are offered for example by Merck under the name Iriodin.
- the Iriodin range from Merck includes pearlescent pigments and metal-oxide-coated mica pigments as well as the subclasses: interference pigments, metallic luster effect pigments (iron oxide coating of the mica core), silver-white effect pigments, Gold gloss effect pigments (titanium oxide and iron oxide coated mica core).
- iriodin types of the Iriodin LS series namely Iriodin LS 820, Iriodin LS 825, Iriodin LS 830, Iriodin LS 835 and Iriodin LS 850.
- Iriodin LS 820 and Iriodin LS 825 are particularly preferred.
- mica or mica pigments titanium dioxide, kaolin, organic and inorganic color pigments, antimony (III) oxide, metal pigments, pigments based on bismuth oxychloride (eg Merck series Biflair, high gloss pigment), indium tin oxide (Nano ITO Powder, from Nanogate Technologies GmbH or AdNano tm ITO of Degussa), AdNano tm zinc oxide (Degussa), lanthanum hexachloride, ClearWeld® (WO 0238677) and commercially available flame retardants which melamine cyanurate or phosphorus, preferably phosphates, phosphites, phosphonites or elemental (red ) Phosphorus.
- bismuth oxychloride eg Merck series Biflair, high gloss pigment
- indium tin oxide Na ITO Powder, from Nanogate Technologies GmbH or AdNano tm ITO of Degussa
- AdNano tm zinc oxide AdNan
- the absorber preferably exhibits interference pigments, particularly preferably from the Iriodin LS series from Merck, or Clearweld®.
- the chemical name for the KHP is copper hydroxide phosphate; This is used as a light green, fine crystalline powder with a mean grain diameter of almost 3 microns.
- the carbon black can be produced by the furnace black process, the gas black process, or the flame black process, preferably by the furnace black process.
- the primary particle size is between 10 and 100 nm, preferably between 20 and 60 nm, the grain distribution can be narrow or wide.
- the BET surface area according to DIN 53601 is between 10 and 600 m 2 / g, preferably between 70 and 400 m 2 / g.
- the soot particles can be oxidatively treated to adjust surface functionalities. They may be hydrophobic (for example Printex 55 or Flegruß 101 from Degussa) or hydrophilic (for example carbon black FW20 or Printex 150 T from Degussa).
- Bone charcoal is a mineral black pigment that contains elemental carbon. It consists of 70 to 90% calcium phosphate and 30 to 10% carbon. The density is typically between 2.3 and 2.8 g / ml.
- the absorber may also contain a mixture of organic and / or inorganic pigments, flame retardants, or other colorants which poorly absorb any electromagnetic waves of their own but, in combination, absorb the registered electromagnetic energy sufficiently well for use in the process of the present invention.
- the absorber can be present, for example, as granules or as a powder. Depending on the method of preparation of the powder suitable for the process according to the invention, they can be ground or reground. If the use of a dispersion is advantageous for the preparation process, the absorber can either already be in the form of a dispersion or a dispersion can be prepared from finely divided absorbent particles.
- the absorber can also be present as a liquid. An example of this is ClearWeld®.
- Such additives which are used here as absorbers, are available, for example, from Merck under the name Iriodin®.
- carbon black are meant commercially available standard blacks, such as those offered by the companies Degussa AG, Cabot Corp., or Continental Carbon.
- Suitable absorbers in general are Iriodin® LS 820 or Iriodin® LS 825 or Iriodin® LS 850 from Merck.
- An example of the carbon black may be Printex 60, Printex A, Printex XE2, or Printex Alpha from Degussa.
- Suitable KHP is also offered by Degussa under the brand name Vestodur FP-LAS.
- Powder according to the invention may also comprise at least one adjuvant, at least one filler and / or at least one pigment.
- adjuvants may be e.g. Flow aids, such as be fumed silica or precipitated silica.
- Pyrogenic silica (fumed silica) is offered by Degussa AG, for example, under the product name Aerosil®, with different specifications.
- powder according to the invention has less than 3% by mass, preferably from 0.001 to 2% by mass and very particularly preferably from 0.05 to 1% by mass of such pigments, based on the total sum of the components, ie the sum of polymers and absorbers.
- the fillers may e.g. Glass, metal, especially aluminum or ceramic particles, e.g. solid or hollow glass beads, steel balls, aluminum balls or metal grit or even colored pigments, such as e.g. Be transition metal oxides.
- the filler particles preferably have a smaller or approximately the same size as the average particle size of the particles of the polymers or the particles coated with polymer.
- the average particle size d 50 of the fillers should preferably not fall below the mean particle size d 50 of the polymers by more than 20%, preferably by not more than 15%, and very particularly preferably by not more than 5%.
- the particle size is in particular limited by the permissible construction height or layer thickness in the layered apparatus used in each case.
- powder according to the invention has less than 75% by mass, preferably from 0.001 to 70% by mass, more preferably from 0.05 to 50% by mass and most preferably from 0.5 to 25% by mass of such fillers, based on the total of the components, so that the volume fraction of the polymers in each case is greater than 50%.
- the volume fraction of the polymers may also be less than 50%.
- the preparation of the powders according to the invention is easily possible and is preferably carried out according to the inventive method for producing powder according to the invention, which is characterized in that a PAEK powder is prepared, optionally, the resulting grain fraction or grain shape is adapted for use in the RP / RM process, further optionally provided subsequently with auxiliaries and additives , And in case of need with an absorber is added.
- the optimal order of the modifications applied to the base material should not be anticipated by the list.
- the auxiliaries and additives or the absorber can be incorporated in the dry blend. It may be advantageous to provide the absorber first alone or else the finished mixture with a flow aid when using a powdered absorber, for example from the Aerosil series of Degussa, z. As Aerosil R972 or R812 or Aerosil 200th
- the powder may be a PAEK powder which is already suitable for rapid prototyping / rapid-manufacturing processes and to which finely divided particles of the absorber are simply added.
- the particles preferably have a smaller to at most approximately equal size average particle size than the polymer-comprising particles.
- the average particle size d 50 of the absorber should preferably be below the mean particle size d 50 of the polymer powders by more than 20%, preferably by more than 50% and very particularly preferably by more than 70%.
- the grain size is limited to the top in particular by the allowable height or layer thickness in the rapid prototyping / rapid-manufacturing plant.
- the absorber has an average particle size of 0.001 to 50 microns, preferably from 0.02 to 10 microns.
- PAEK powders which are characterized by a high BET surface area
- a very good distribution of the absorber is given.
- pigments which are distributed on a relatively smooth surface of particles with a BET surface area below 1 m 2 / g, lead to a sharp decrease in the mechanical properties of the components produced therewith.
- the elongation at break suffers from the predetermined breaking points, which represents the pigment concentration on the surface.
- a suitable flow aid such as pyrogenic alumina, fumed silica or pyrogenic titanium dioxide, the precipitated or ground powder may be added externally to the powder of the invention to improve the trickle.
- a finely divided mixing can be carried out in the simplest embodiment of the method according to the invention, for example by mixing finely powdered absorber on the dry powder in high-speed mechanical mixers.
- inorganic pigments in particular colored pigments, such as e.g. Transition metal oxides, stabilizers, e.g. Phenols, in particular sterically hindered phenols, flow and flow aids, such. fumed silicas and filler particles are added.
- colored pigments such as e.g. Transition metal oxides
- stabilizers e.g. Phenols, in particular sterically hindered phenols
- flow and flow aids such. fumed silicas and filler particles are added.
- concentrations for fillers and / or auxiliaries stated for the powder according to the invention are maintained.
- a mixture is prepared as a powder, in addition to the PAEK particles and various fillers such.
- various fillers such as glass particles, ceramic particles or metal particles, or other additives such as flame retardants.
- Typical fillers are z.
- the filler particles in this case preferably have a smaller or approximately the same size as the average particle size of the PAEK-comprising particles.
- the average particle size d 50 of the fillers should not exceed the average particle size d 50 of the PAEK-containing particles by more than 20%, preferably by not more than 15% and most preferably by not more than 5%.
- the particle size is limited by the permissible structural height or layer thickness in a RP / RM apparatus suitable for the method described above (RP / RM method).
- glass spheres with a mean diameter of 20 to 80 microns are used.
- Another preferred range is average particle sizes for the fillers or additives below 20 microns, preferably below 15 microns.
- the present invention also provides the use of inventive powder for the production of moldings in a layer-by-layer and selectively melting the powder (rapid prototyping or rapid-manufacturing) method, in which powders according to the invention, which may additionally be modified as described, and / or have an absorber can be used.
- the present invention is the use of the PAEK powder according to the invention, which may additionally be modified as described and / or may have an absorber for the production of moldings by selective laser sintering.
- the laser-sintering processes are well known and rely on the selective sintering of polymer particles whereby layers of polymer particles are briefly exposed to laser light, thus fusing the polymer particles exposed to the laser light.
- the successive sintering of layers of polymer particles produces three-dimensional objects. Details of the method of selective laser sintering can be found, for example, in the specifications US Pat. No. 6,136,948 and WO 96/06881.
- the wavelength of the commonly used CO 2 laser is 10600 nm.
- the erfmdungssiee powder in particular if it has an absorber, but also in processes which laser with a wavelength between 100 and 3000 nm, preferably between 800 and 1070 nm or between 1900 and 2100 nm, used, in particular in that described above.
- the powder according to the invention can be used in particular for the production of shaped bodies from powders by the SLS method (laser selective sintering) by means of lasers with a wavelength of 10600 nm, and between 100 and 3000 nm, preferably between 800 and 1070 nm or between 1900 and 2100 nm, be used.
- Laser energy with wavelengths between 100 and 3000 nm can usually be easily coupled into an optical waveguide. This eliminates the need for sophisticated mirror systems, if this optical fiber can then be performed flexibly over the site. Further bundling of the laser beam can take place via lenses or mirrors. Also, a cooling of the laser is not required in all cases.
- the shaped bodies according to the invention produced by a process for the layered construction of three-dimensional objects, in which areas of a powder layer, in particular of the powder according to the invention, are selectively melted by the action of electromagnetic waves, e.g. Selective laser sintering, characterized in that they have PAEK. Particularly preferably, they have a PEEK, PEK, PEKK, or a PEEKK.
- the absorber optionally present in the shaped article according to the invention may have, for example, a so-called colorant.
- a colorant is understood to mean all colorants according to DIN 55944, which can be classified into inorganic and organic colorants and into natural and synthetic colorants (see Rompps Chemielexikon, 1981, 8th edition, page 1237).
- DIN 55943 Sept. 1984
- DIN 55945 Advantix achromatic colorant
- Dyes are soluble in solvents and / or binders inorganic or organic, colored or achromatic colorants.
- the absorber optionally present in the shaped body according to the invention can also obtain its absorbing effect by having additives.
- additives may be, for example, melamine cyanurate based flame retardants (Melapur from the DSM) or based on phosphorus, preferably phosphates, phosphites, phosphonites or elemental red phosphorus.
- melamine cyanurate based flame retardants Melapur from the DSM
- phosphorus preferably phosphates, phosphites, phosphonites or elemental red phosphorus.
- carbon fibers preferably ground, glass beads, also hollow, or kaolin, chalk, wollastonite, or graphite.
- the absorber optionally present in the shaped article according to the invention preferably comprises carbon black or KHP (copper hydroxide phosphate) or chalk, bone charcoal, carbon fibers, graphite, flame retardants or interference pigments as the main component.
- Interference pigments are so-called pearlescent pigments. Based on the natural mineral mica, they are coated with a thin layer of metal oxides, for example titanium dioxide and / or iron oxide, and are available with a mean particle size distribution between 1 and 60 ⁇ m. Interference pigments are offered for example by Merck under the name Iriodin.
- the Iriodin range from Merck includes pearlescent pigments and metal oxide-coated mica pigments as well as the subclasses: interference pigments, metallic luster effect pigments (iron oxide coating of the mica core), silver-white effect pigments, gold-luster effect pigments (mica core coated with titanium dioxide and iron oxide).
- iriodin types of the Iriodin LS series namely Iriodin LS 820, Iriodin LS 825, Iriodin LS 830, Iriodin LS 835 and Iriodin LS 850.
- Iriodin LS 820 and Iriodin LS 825 are particularly preferred.
- the absorber optionally present in the shaped article according to the invention can be, for example, mica or mica pigments, titanium dioxide, kaolin, organic and inorganic color pigments, Antimony (111) oxide, metal pigments, bismuth oxychloride-based pigments (eg Merck's Biflair series, high gloss pigment), indium tin oxide (Nano ITO powder, from Nanogate Technologies GmbH or AdNano tm ITO of Degussa), AdNano tm zinc oxide ( Degussa), lanthanum hexachloride, ClearWeld® (WO 0238677) and commercially available flame retardants which melamine cyanurate or phosphorus, preferably phosphates, phosphites, phosphonites or elemental (red) phosphorus.
- melamine cyanurate or phosphorus preferably phosphates, phosphites, phosphonites or elemental (red) phosphorus.
- the shaped body according to the invention based on the sum of the components present in the shaped body, preferably has from 0.01 to 30% by mass of absorber, preferably from 0.05 to 20% by mass, particularly preferably from 0.2 to 15% by mass. and most preferably from 0.4 to 10% by mass.
- the maximum amount of absorber is 50% by mass, based on the sum of the components present in the molding.
- the shaped articles can also contain fillers and / or auxiliaries and / or pigments, such as, for example, thermal stabilizers and / or oxidation stabilizers, e.g. have sterically hindered phenol derivatives.
- Fillers may e.g. Glass, ceramic particles and metal particles such as iron balls, or corresponding hollow balls be.
- the shaped bodies according to the invention preferably have glass particles, very particularly preferably glass spheres.
- moldings according to the invention have less than 3% by weight, preferably from 0.001 to 2% by mass and very particularly preferably from 0.05 to 1% by mass, of such auxiliaries, based on the sum of the components present.
- shaped bodies less than 75 mass%, preferably from 0.001 to 70 mass%, particularly preferably from 0.05 to 50 mass% and most preferably from 0.5 to 25 mass% of such fillers based on the Sum of existing components.
- the determination of the BET surface area carried out in the following examples was carried out according to DIN 66 131.
- the bulk density was determined using an apparatus according to DIN 53 466.
- the laser diffraction measurements were taken on a Malvern Mastersizer S, Ver. 2.18 received.
- Particles of PEEK with a BET surface area of 50 m 2 / g and a mean grain diameter of 500 ⁇ m were ground using a cryogenic pin mill (Hosokawa Alpine CW 160).
- the PEEK particles were conveyed via a screw conveyor into a grinding chamber and cooled down to -50 ° C with liquid nitrogen.
- the PEEK particles were accelerated by rotating pin disks to 220 m / s. At this speed, they impacted the pins on the pin disks, exposing them to strong impact, causing the particles to break. This happened with a throughput of PEEK particles of 15 kg / h.
- the grinding chamber left a micronized product with a proportion of particles smaller than 100 microns of 30 wt .-% (sieve analysis with Alpine air jet sieve according to DIN EN ISO 4610).
- the process cut of separation followed.
- the crushed PEEK particles were fractionated using an Alpine air jet screen with a downstream cyclone.
- the fractionation was carried out at a mesh size of 80 microns.
- the thus obtained Powder was characterized by a d 10 of 16.7 ⁇ m, d 50 of 52.6 ⁇ m and d 90 of 113.8 ⁇ m.
- Example 3 PEEK powder with Iriodin® LS 825
- Example 5 PEEK powder Victrex 450 G ground (not according to the invention)
- Example 6 Processing in an apparatus with Nd: YAG laser
- a 10x10 cm open-top box was provided with a bottom, which is movable via a spindle.
- the floor was moved to half an inch to the top edge; the remaining space was filled with powder and smoothed with a metal plate.
- the apparatus was placed in the installation space of a Nd: YAG laser Star Mark 65 (manufacturer Carl Basel Laser Technology).
- a 4 mm wide and 20 mm long surface was melted by the laser.
- the next steps, rotation of the spindle to lower the ground by 0.15 mm and application of the next powder layer, smooth down, and then re-exposing the 4 mm wide and 20 mm long surface by the Nd: YAG laser to melt the powder were repeated several times.
- Example 7 Processing in an EOSINT P 360
- the powders from Examples 2-5 were tested in the laser sintering machine of the manufacturer EOS GmbH, Krailling, in Germany. Work was carried out with the maximum possible installation space temperature of approx. 200 ° C. The powder of Example 5 had no processing window. Although the maximum possible energy was introduced, there was no smooth melt film, but a spotty surface on which the individual grains were still visible. A second layer could not be applied because there was strong curl at the edges of the film, that is, curling up the edges out of the build plane. When the laser power was increased in the direction of the maximum value for the 50-watt laser, ash particles formed, which settled on the build platform. The powder of Example 2 could be processed, however, a platelet was formed, which had relatively many voids, which was reflected in the low density. The powders of Examples 3 and 4 could be processed and produced much denser components than the powder of Example 2. Density [g / l] Component of powder of Example 2 0.91 Component of powder from Example 3 1.1 Component of powder from Example 4 1.21
- the heat resistance of the components of Examples 3 and 4 was according to DIN 53461, HDTB 218 or 221 ° C.
- a laser-sintered component made of the standard material EOSINT P2200 GF has a heat resistance of 140 ° C.
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Abstract
Description
Die zügige Bereitstellung von Prototypen ist eine in der jüngsten Zeit häufig gestellte Aufgabe. Besonders geeignet sind Verfahren, die auf der Basis von pulverförmigen Werkstoffen arbeiten, und bei denen schichtweise durch selektives Aufschmelzen und Verfestigen die gewünschten Strukturen hergestellt werden. Die Verfahren sind aber auch für die Herstellung von Kleinserien geeignet.The speedy provision of prototypes is a common task in recent times. Particularly suitable are processes which work on the basis of powdery materials, and in which the desired structures are produced in layers by selective melting and solidification. The methods are also suitable for the production of small batches.
Die Erfindung betrifft die Verwendung eines porösen Polyarylenetherketon (PAEK) mit einer BET-Oberfläche zwischen 1 und 60 m2/g, bevorzugt zwischen 5 und 45 m2/g, besonders bevorzugt zwischen 15 und 40 m2/g, das zu einem Pulver vermahlen wird, sowie Modifizierungen dieses Pulvers, die Verwendung desselben in einem schichtweise arbeitenden Verfahren, mit welchem selektiv Bereiche einer pulverförmigen Schicht durch Eintrag elektromagnetischer Energie aufgeschmolzen werden, sowie Formkörper, hergestellt durch ein oben genanntes Verfahren.The invention relates to the use of a porous polyarylene ether ketone (PAEK) having a BET surface area between 1 and 60 m 2 / g, preferably between 5 and 45 m 2 / g, particularly preferably between 15 and 40 m 2 / g, that to a powder as well as modifications of this powder, the use thereof in a layer-by-layer process with which selectively areas of a powdery layer are melted by introduction of electromagnetic energy, and moldings produced by a method mentioned above.
Das poröse PAEK wird in der Regel hergestellt durch Umsetzung einer aromatischen Dihalogenverbindung mit einem Bisphenol und/oder eines Halogenphenols in Gegenwart von Alkali- oder Erdalkalicarbonat oder ―hydrogencarbonat in einem hochsiedenden aprotischen Lösemittel zu einem PAEK, Austragen und Erstarrenlassen der Schmelze, gegebenenfalls Mahlen, z. B. in einer Hammermühle, Extrahieren der entstandenen Partikel mit einem oder mehreren organischen Lösemitteln zwecks Entfernung des Reaktionslösemittels sowie mit Wasser zwecks Entfernung der anorganischen Salze, und anschließendes Trocknen. Die zu extrahierenden Partikel können aus dem Reaktionsgemisch außer durch Mahlen auch durch Granulieren eines extrudierten Strangs, Tropfenauftrag auf ein gekühltes Metallband, Prillen oder Sprühtrocknen hergestellt werden. Der Grad der nach der Extraktion erhaltenen Porosität hängt insbesondere vom Gehalt an Reaktionslösemittel im zu extrahierenden Gut ab. Insofern ist es vorteilhaft, beim Sprühtrocknen nur einen Teil des Reaktionslösemittels zu entfernen. Ansonsten ist die Art, wie die zu extrahierenden Partikel erzeugt werden, unkritisch.The porous PAEK is usually prepared by reacting an aromatic dihalogen compound with a bisphenol and / or a halophenol in the presence of alkali or alkaline earth carbonate or bicarbonate in a high boiling aprotic solvent to a PAEK, discharging and solidifying the melt, optionally grinding, z , In a hammer mill, extracting the resulting particles with one or more organic solvents to remove the reaction solvent and with water to remove the inorganic salts, and then drying. The particles to be extracted may be prepared from the reaction mixture other than by milling, also by granulating an extruded strand, applying a drop to a chilled metal strip, prilling or spray-drying. The degree of porosity obtained after the extraction depends in particular on the content of reaction solvent in the material to be extracted. In this respect, it is advantageous to remove only a portion of the reaction solvent during spray drying. Otherwise, the way in which the particles to be extracted are produced is not critical.
Das Herstellverfahren von PAEK mit anschließender Extraktion ist in einer großen Anzahl von Patentanmeldungen beschrieben, beispielsweise EP-A-0 001 879, EP-A-0 182 648, EP-A-0 244 167 und EP-A-0 322 151.The manufacturing process of PAEK with subsequent extraction is in a large number of Patent applications, for example EP-A-0 001 879, EP-A-0 182 648, EP-A-0 244 167 and EP-A-0 322 151.
Im Rahmen der Erfindung kann jedoch auch ein PAEK, das eventuell nach einem anderen Verfahren hergestellt wurde und das in kompakter Form vorliegt, z. B. als Granulat, in einem geeigneten hochsiedenden aprotischen Lösemittel aufgelöst werden, worauf die heiße Lösung, so wie oben für die bei der Reaktion erhaltene Schmelze beschrieben, in Partikelform überführt und mit einem oder mehreren organischen Lösemitteln extrahiert wird.In the context of the invention, however, a PAEK, which was possibly produced by a different process and which is in a compact form, for. As granules are dissolved in a suitable high-boiling aprotic solvent, whereupon the hot solution, as described above for the melt obtained in the reaction, converted into particle form and extracted with one or more organic solvents.
Das hochsiedende aprotische Lösemittel ist gemäß dem Stand der Technik vorzugsweise eine Verbindung der Formel
Das PAEK enthält Einheiten der Formeln
(-Ar-X-) und (-Ar'-Y-),
wobei Ar und Ar' einen zweiwertigen aromatischen Rest darstellen, vorzugsweise 1,4-Phenylen, 4,4'-Biphenylen sowie 1,4- 1,5- oder 2,6-Naphthylen. X ist eine elektronenziehende Gruppe, bevorzugt Carbonyl oder Sulfonyl, während Y eine Gruppe wie O, S, CH2, Isopropyliden oder dergleichen darstellt. Hierbei sollten mindestens 50 %, bevorzugt mindestens 70 % und besonders bevorzugt mindestens 80 % der Gruppen X eine Carbonylgruppe darstellen, während mindestens 50 %, bevorzugt mindestens 70 % und besonders bevorzugt mindestens 80 % der Gruppen Y aus Sauerstoff bestehen sollten.The PAEK contains units of the formulas
(-Ar-X-) and (-Ar'-Y-),
wherein Ar and Ar 'represent a bivalent aromatic radical, preferably 1,4-phenylene, 4,4'-biphenylene and 1,4- 1,5- or 2,6-naphthylene. X is an electron-withdrawing group, preferably carbonyl or sulfonyl, while Y represents a group such as O, S, CH 2 , isopropylidene or the like. This should be at least 50%, preferably at least 70% and especially preferably at least 80% of the groups X represent a carbonyl group, while at least 50%, preferably at least 70% and particularly preferably at least 80% of the groups Y should consist of oxygen.
In der insbesondere bevorzugten Ausfixhrungsform bestehen 100 % der Gruppen X aus Carbonylgruppen und 100 % der Gruppen Y aus Sauerstoff. In dieser Ausführungsform kann das PAEK beispielsweise ein Polyetheretherketon (PEEK; Formel I), ein Polyetherketon (PEK; Formel II), ein Polyetherketonketon (PEKK; Formel III) oder ein Polyetheretherketonketon (PEEKK; Formel IV) sein, jedoch sind natürlich auch andere Anordnungen der Carbonyl- und Sauerstoffgruppen möglich.
Das PAEK ist im Allgemeinen teilkristallin, was sich beispielsweise in der DSC-Analyse durch Auffinden eines Kristallitschmelzpunkts Tm äußert, der größenordnungsmäßig in den meisten Fällen um 300 °C oder darüber liegt. Jedoch ist die Lehre der Erfindung auch auf amorphe PAEK anwendbar. Im Allgemeinen gilt, dass Sulfonylgruppen, Biphenylengruppen, Naphthylengruppen oder sperrige Gruppen Y, wie z. B. eine Isopropylidengruppe, die Kristallinität verringern.The PAEK is generally semicrystalline, as evidenced, for example, in the DSC analysis by finding a crystalline melting point T m , which is of the order of magnitude of 300 ° C or higher in most cases. However, the teaching of the invention is also applicable to amorphous PAEK. In general, it is true that sulfonyl groups, biphenylene groups, naphthylene groups or bulky groups Y, such as. As an isopropylidene group, reduce the crystallinity.
In einer bevorzugten Ausführungsform beträgt die Viskositätszahl, gemessen entsprechend DIN EN ISO 307 an einer Lösung von 250 mg PAEK in 50 ml 96-gewichtsprozentiger H2SO4 bei 25 °C, etwa 20 bis 150 cm3/g und bevorzugt 50 bis 120 cm3/g.In a preferred embodiment, the viscosity number, measured according to DIN EN ISO 307 on a solution of 250 mg PAEK in 50 ml of 96 weight percent H 2 SO 4 at 25 ° C, about 20 to 150 cm 3 / g and preferably 50 to 120 cm 3 / g.
Die BET-Oberfläche wird gemäß DIN ISO 66131 bestimmt.The BET surface area is determined according to DIN ISO 66131.
Das poröse PAEK kann bei Raumtemperatur oder erhöhter Temperatur vermahlen werden, jedoch ist es zur Verbesserung der Vermahlung und der Mahlausbeute vorteilhaft, bei tieferer Temperatur zu vermahlen, bevorzugt unterhalb von 0 °C, besonders bevorzugt unterhalb von -20 °C und insbesondere bevorzugt unterhalb von -40 °C. Zum Vermahlen eignen sich unter anderem Stiftrnühlen, Fließbettgegenstrahlmühlen oder Pralltellermühlen. Hierbei sorgt die poröse Struktur des zu mahlenden PAEK für Schwachstellen, die unter den obengenannten Bedingungen zum Bruch führen.The porous PAEK may be milled at room temperature or elevated temperature, but to improve milling and milling yield it is advantageous to grind at a lower temperature, preferably below 0 ° C, more preferably below -20 ° C, and most preferably below -40 ° C. For milling, among other things, pin mill, fluidized bed opposed jet mills or baffle mills are suitable. In this case, the porous structure of the PAEK to be grounded provides weak points which lead to breakage under the abovementioned conditions.
Das Mahlgut kann nachträglich gesichtet oder gesiebt werden. Je nach eingesetztem Mahlgut und anschließendem Trennverfahren kann ein feinpulvriges für das erfindungsgemäße Verfahren einsetzbare PAEK mit einem zahlenmittleren Partikeldurchmesser (d50) von 30 bis 150 µm, bevorzugt von 45 bis 120 µm, besonders bevorzugt von 48 bis 100 µm hergestellt werden.The regrind can be subsequently screened or sieved. Depending on the millbase used and subsequent separation process, a finely powdered PAEK which can be used for the process according to the invention can be produced with a number-average particle diameter (d 50 ) of 30 to 150 μm, preferably 45 to 120 μm, particularly preferably 48 to 100 μm.
Die Bestimmung der Teilchendurchmesser und deren Verteilung erfolgt durch Laserbeugung nach DIN ISO 13320-1.The determination of the particle diameter and its distribution is carried out by laser diffraction according to DIN ISO 13320-1.
Zur Herstellung der erfmdungsgemäßen Formteile sind Verfahren besonders geeignet, die auf der Basis von pulverförmigen thermoplastischen Werkstoffen arbeiten, und bei denen schichtweise durch selektives Aufschmelzen und Verfestigen die gewünschten Strukturen hergestellt werden. Auf Stützkonstruktionen bei Überhängen und Hinterschnitten kann dabei verzichtet werden, da das die aufgeschmolzenen Bereiche umgebende Pulverbett ausreichende Stützwirkung bietet. Ebenso entfällt die Nacharbeit, Stützen zu entfernen. Die Verfahren sind auch für die Herstellung von Kleinserien geeignet.For the production of the molded parts according to the invention, processes are particularly suitable which work on the basis of pulverulent thermoplastic materials and in which the desired structures are produced in layers by selective melting and solidification. On support structures for overhangs and undercuts can be dispensed with, since the powder bed surrounding the molten areas provides sufficient support effect. It also eliminates the rework to remove columns. The methods are also suitable for the production of small batches.
Die Erfindung betrifft ein Verfahren zur Verwendung eines Pulvers auf Basis von PAEK sowie Formkörper, hergestellt durch ein schichtweise arbeitendes Verfahren, mit welchem selektiv Bereiche einer Schicht durch Eintrag elektromagnetischer Energie aufgeschmolzen werden, unter Verwendung dieses Pulvers. Die aufgeschmolzenen Bereiche verfestigen sich beim Abkühlen und bilden dabei den gewünschten Formkörper. Überschüssiges Pulvermaterial wird entfernt.The invention relates to a process for using a powder based on PAEK and molded articles, produced by a layer-by-layer process, with which selectively areas of a layer are melted by applying electromagnetic energy, using this powder. The melted areas solidify on cooling, thereby forming the desired shaped body. Excess powder material is removed.
Ein Verfahren, welches besonders gut für den Zweck des Rapid-Prototyping bzw. Rapid-Manufacturing geeignet ist, ist das Laser-Sintern. Bei diesem Verfahren werden Kunststoffpulver in einer Kammer selektiv kurz mit einem Laserstrahl belichtet, wodurch die Pulverpartikel, die von dem Laserstrahl getroffen werden, schmelzen. Die geschmolzenen Partikel laufen ineinander und erstarren nach dem Abkühlen wieder zu einer festen Masse. Durch wiederholtes Belichten von immer neu aufgebrachten Schichten können mit diesem Verfahren komplexe dreidimensionale Körper einfach und schnell hergestellt werden.One method which is particularly well suited for the purpose of rapid prototyping or rapid manufacturing is laser sintering. In this method, plastic powders in a chamber are selectively exposed briefly to a laser beam, thereby melting the powder particles that are hit by the laser beam. The molten particles run into each other and solidify after cooling back to a solid mass. By repeatedly exposing layers that are always newly applied, this method can be used to produce complex three-dimensional solids quickly and easily.
Neben dem Lasersintern gibt es jedoch eine Reihe weiterer geeigneter Verfahren. Die Selektivität der schichtweise arbeitenden Verfahren kann dabei über die Auftragung von Suszeptoren, Absorber, Inhibitoren, oder durch Masken, oder über fokussierte Energieeinbringung, wie beispielsweise durch einen Laserstrahl oder durch ein Glasfaserkabel erfolgen.In addition to laser sintering, however, there are a number of other suitable methods. The selectivity of the layered processes can be done via the application of susceptors, absorbers, inhibitors, or by masks, or via focused energy input, such as by a laser beam or by a fiber optic cable.
Im Folgenden werden einige Verfahren beschrieben, mit denen aus dem erfindungsgemäßen Pulver erfindungsgemäße Formteile hergestellt werden können, ohne dass die Erfindung darauf beschränkt werden soll.In the following, some methods are described with which molded parts according to the invention can be produced from the powder according to the invention, without the invention being restricted thereto.
Das Verfahren des Laser-Sinterns (Rapid Prototyping) zur Darstellung von Formkörpern aus pulverförmigen Polymeren wird ausführlich in der Patentschriften US 6,136,948 und WO 96/06881 (beide DTM Corporation) beschrieben. Eine Vielzahl von Polymeren und Copolymeren wird für diese Anwendung beansprucht, wie Polyacetat, Polypropylen, Polyethylen, Ionomere und Polyamid 11.The process of laser sintering (rapid prototyping) for the preparation of molded articles from pulverulent polymers is described in detail in US Pat. Nos. 6,136,948 and WO 96/06881 (both DTM Corporation). A variety of polymers and copolymers are claimed for this application, such as polyacetate, polypropylene, polyethylene, ionomers and polyamide 11.
Beim Lasersinterprozess entsteht ein blockartiger Körper, der zum einen aus den gewünschten Bauteilen besteht, zum anderen und meist überwiegenden Teil aus nicht belichtetem Pulver, sogenanntem Rückpulver, welches bis zum Entformen bzw. Auspacken mit den Bauteilen in diesem Block verbleibt. Es hat eine stützende Wirkung auf die Bauteile, so dass Überhänge und Hinterschnitte mit dem Lasersinterverfahren ohne Stützkonstruktionen realisierbar sind. Je nach Art des verwendeten Pulvers kann das nicht belichtete Pulver nach Sieben und Zugabe von Neupulver in einem weiteren Bauprozess eingesetzt werden (Recycling).The laser sintering process produces a block-like body, which consists of the desired components on the one hand and, for the most part, predominantly unexposed powder, so-called powdered powder, which remains in this block until demoulding or unpacking with the components. It has a supporting effect on the components, so that overhangs and undercuts can be realized with the laser sintering process without supporting structures. Depending on the type of powder used, the unexposed powder can be used in a further building process after sieving and addition of new powder (recycling).
Andere gut geeignete Verfahren sind das SIV-Verfahren wie es in WO 01/38061 beschrieben, oder ein Verfahren wie inEP1015214 beschrieben. Beide Verfahren arbeiten mit einer Infrarotheizung zum Aufschmelzen des Pulvers. Die Selektivität des Aufschmelzens wird bei ersterem durch die Auftragung eines Inhibitors, beim zweiten Verfahren durch eine Maske erreicht. Ein weiteres Verfahren ist in DE 103 11 438 beschrieben. Bei diesem wird die zum Verschmelzen benötigte Energie durch einen Mikrowellengenerator eingebracht und die Selektivität wird durch Auftragen eines Suszeptors erreicht. Weitere geeignete Verfahren sind solche, die mit einem Absorber arbeiten, der entweder im Pulver enthalten ist, oder der per Inkjet-Verfahren aufgetragen wird wie in DE 102004012682.8, DE 102004012683.6 und DE 102004020452.7. beschrieben. Dabei kann zur Einwirkung der elektromagnetischen Energie eine große Bandbreite an Lasern verwendet werden, aber auch eine flächige Einwirkung der elektromagnetischen Energie ist geeignet.Other well-suited methods are the SIV method as described in WO 01/38061 or a method as described in EP1015214. Both methods use an infrared heater to melt the powder. The selectivity of the melting is achieved in the former by the application of an inhibitor, in the second method by a mask. Another method is described in DE 103 11 438. In this, the energy required for fusing is introduced by a microwave generator and the selectivity is achieved by applying a susceptor. Further suitable methods are those which work with an absorber which is either contained in the powder or which is applied by inkjet method as in DE 102004012682.8, DE 102004012683.6 and DE 102004020452.7. described. In this case, a large bandwidth of lasers can be used for the action of the electromagnetic energy, but even a surface action of the electromagnetic energy is suitable.
In "Selective Laser Sintering of Nylon 12-Peek Blends formed by cryogenic mechanical alloying", von J. P. Schultz, J. P. Martin, R. G. Kander, veröffentlicht in den Solid Freeform Fabrication Proceedings 2000, Seiten 119-124, wird ein Blend aus Nylon 12 und PEEK beschrieben, welches einen mechanischen Blendprozeß bei tiefen Temperaturen beschreibt, wobei beide Komponenten in Pulverform vorliegen. Dabei wird bereits die Schwierigkeit, deutlich, ein dichtes Bauteil per Lasersintern mit dem Blend zu erzeugen.In "Selective Laser Sintering of Nylon 12-Peek Blends Formed by Cryogenic Mechanical Alloying", JP Schultz, JP Martin, RG Kander, published in the Solid Freeform Fabrication Proceedings 2000, pp. 119-124, discloses a blend of Nylon 12 and PEEK which describes a mechanical blending process at low temperatures, both components being in powder form. This already makes the difficulty, clearly, to produce a dense component by laser sintering with the blend.
Nachteilig beim Stand der Technik ist, dass ein hochwärmeformbeständiges Material für die Verwendung in einem dreidimensionalen Verfahren, bei welchem schichtweise aufgetragenes pulverförmiges Material selektiv mit Hilfe von elektromagnetischen Wellen aufgeschmolzen wird und nach dem Abkühlen die gewünschte dreidimensionale Struktur bildet, bisher nicht kommerziell zur Verfügung stand. Die Ursache liegt zum einen in der Schwierigkeit, ein ausreichend feines Pulver zu erzeugen. Ausreichend fein heißt, dass der gewünschte Auflösungsgrad der Bauteile erreicht wird, und gleichzeitig die Schichtdicke gering genug ist, dass die selektiv eingebrachte Energie ausreicht, um das Aufschmelzen einer Schicht zu gewährleisten. Als Beispiel für den mittleren Korndurchmesser eines Pulvers zur Verwendung in einem der beschriebenen Verfahren kann der Bereich von 30 bis 150 µm genannt werden. Ausbeuten bei der Vermahlung von weniger als 10 % sind in der Regel nicht als kommerziell nutzbare Lösung anzusehen. Zum anderen liegen die Temperaturen, bei denen speziell die hochwärmeformständigen Materialien verarbeitet werden, sehr hoch und sind daher schwierig bis gar nicht in den am Markt befindlichen Rapid-Prototyping/Rapid-Manufacturing-Maschinen zu verarbeiten. Neben den hohen Schmelztemperaturen liegt die Ursache auch in den sehr niedrigen BET-Oberflächen eines PAEK-Pulvers nach dem Stand der Technik, die zu einer verschlechterten Energieaufnahme des aufzuschmelzenden Partikels führen.A disadvantage of the prior art is that a highly heat-resistant material for use in a three-dimensional process in which layered powdered material is selectively melted by means of electromagnetic waves and forms the desired three-dimensional structure after cooling, has not been commercially available. The reason lies firstly in the difficulty of producing a sufficiently fine powder. Sufficiently fine means that the desired degree of dissolution of the components is achieved, and at the same time the layer thickness is low enough that the selectively introduced energy is sufficient to ensure the melting of a layer. As an example of the average grain diameter of a powder for use in any of the described methods, the range of 30 to 150 μm may be cited. Yields in the milling of less than 10% are generally not regarded as a commercially usable solution. On the other hand, the temperatures at which especially the high-temperature-deforming materials are processed are very high and are therefore difficult or even impossible to process in the rapid prototyping / rapid-manufacturing machines on the market. In addition to the high melting temperatures, the cause is also in the very low BET surface areas of a PAEK powder according to the prior art, which lead to a deteriorated energy absorption of the particle to be melted.
Überraschend wurde nun, wie in den Ansprüchen beschrieben, gefunden, dass ein Pulver, wie oben beschrieben, sich als Basismaterial zum Einsatz in den beschriebenen dreidimensionalen Verfahren einsetzen läßt. Die mit diesem Pulver hergestellten Teile weisen eine höhere mechanische Festigkeit und höhere Wärmeformbeständigkeit auf als Bauteile aus beispielsweise dem zur Zeit erhältlichen Standardmaterial EOSINT P2200 (Anbieter EOS GmbH, Krailling, Deutschland) oder Duraform (Anbieter 3D-Systems, Valencia, Californien) für Lasersintern. Bevorzugt wird das Material bezüglich der Kornverteilung optimiert und mit einer Rieselhilfe nach dem Stand der Technik ausgerüstet eingesetzt. Auch eine Nachverrundung der durch den Mahlprozeß scharfkantig ausgeprägten Partikel durch mechanische Einwirkung beispielsweise in einem schnelllaufenden Mischer kann vorteilhaft sein. Besonders bevorzugt ist die Ausrüstung der aufzuschmelzenden Pulverbereiche mit einem IR-Absorber, der beispielsweise im Pulver bereits enthalten sein kann oder während der Verarbeitung durch Auftrag des Absorbers per Inkjet-Verfahren oder Streu- oder Sprühverfahren auf die aufzuschmelzenden Bereiche erfolgt.Surprisingly, it has now been found, as described in the claims, that a powder, as described above, can be used as a base material for use in the described three-dimensional process. The parts produced with this powder have a higher mechanical strength and higher heat distortion resistance than components from, for example, the currently available standard material EOSINT P2200 (supplier EOS GmbH, Krailling, Germany) or Duraform (provider 3D-Systems, Valencia, California) for laser sintering. Preferably, the material is optimized with respect to the grain distribution and used equipped with a Rieselhilfe according to the prior art. A subsequent rounding of the sharp-edged by the grinding process particles by mechanical action, for example in a high-speed mixer may be advantageous. Particular preference is given to equipping the powder regions to be melted with an IR absorber, which may already be present in the powder, for example, or during processing by application of the absorber to the areas to be melted by inkjet method or scattering or spraying method.
Basismaterial ist ein Mahlpulver auf der Basis von PAEK (Polyarylenetherketon). Es ist gekennzeichnet durch die Vermahlung von PAEK-Partikeln, die eine BET-Oberfläche von mindestens 1 m2/g aufweisen. Bevorzugt kann es sich dabei um PEEK, PEK, PEKK, oder PEEKK handeln. Der mittlere Korndurchmesser d50 für die Verwendung in einem dreidimensionalen Verfahren, welches auf der Basis von pulverförmigen thermoplastischen Werkstoffen arbeitet, und bei dem schichtweise durch selektives Aufschmelzen und Verfestigen die gewünschten Strukturen hergestellt werden, liegt zwischen 30 und 150 µm, bevorzugt zwischen 45 und 120 µm, und ganz besonders bevorzugt zwischen 48 und 100 µm. Zur besseren Verarbeitbarkeit auf einer Rapid-Prototyping/Rapid-Manufacturing-Anlage kann der Anteil an Partikeln kleiner als 30 µm beispielsweise durch Sichten reduziert werden. Ebenso kann es sinnvoll sein, Partikel, die größer oder nur wenig kleiner sind als die in dem Verfahren eingestellte Schichtdicke, zum Beispiel mit Hilfe einer Siebung zu entfernen. Die Kornverteilung des im RP/RM-Verfahren verwendeten erfindungsgemäßen Pulvers kann dabei eng, breit, oder auch bimodal sein.Base material is a grinding powder based on PAEK (polyarylene ether ketone). It is characterized by the milling of PAEK particles having a BET surface area of at least 1 m 2 / g. This may preferably be PEEK, PEK, PEKK, or PEEKK. The average particle diameter d50 for use in a three-dimensional process, which works on the basis of powdered thermoplastic materials, and in which the desired structures are produced in layers by selective melting and solidification, is between 30 and 150 .mu.m, preferably between 45 and 120 .mu.m , and most preferably between 48 and 100 microns. For better processability on a rapid prototyping / rapid-manufacturing system, the proportion of particles smaller than 30 .mu.m can be reduced, for example by sifting. It may also be useful to remove particles which are larger or only slightly smaller than the layer thickness set in the process, for example by means of sieving. The particle size distribution of the powder according to the invention used in the RP / RM process can be narrow, broad or even bimodal.
Das PAEK-Pulver, welches als Basis für die vorliegende Erfindung dient, weist eine BET-Oberfläche zwischen 1 m2/g und 60 m2/g auf, bevorzugt zwischen 5 m2/g und 45 m2/g, und besonders bevorzugt zwischen 15 m2/g und 40 m2/g. Die große Oberfläche führt zu einer besseren und gleichmäßigeren Aufnahme der elektromagnetischen Energie, die zum selektiven Aufschmelzen von Bereichen einer Pulverschicht benötigt wird. Im Umkehrschluß bedeutet das, dass bei der Verwendung erfindungsgemäßen Pulvers mit geringerer Energie gearbeitet werden kann, und die Bauteile durch den geringeren Energieeintrag weniger Wärmeleitung in umgebende Bereiche zeigen und damit maßgenauer sind. Insbesondere die Problematik der "runden Ecken" bzw. des Wachsens von Bauteilen in Bereichen hohen Wärmeeintrags wird weitgehend vermieden. Mit PAEK-Pulvern nach dem Stand der Technik, die BET-Oberflächen von weniger als 1 m2/g aufweisen, wird dieser Effekt nicht erreicht. Der Kristallitschmelzpunkt des erfindungsgemäßen Pulvers hängt vom verwendetem Typ des PAEK ab; er liegt oberhalb von 300 °C.The PAEK powder which serves as a basis for the present invention has a BET surface area between 1 m 2 / g and 60 m 2 / g, preferably between 5 m 2 / g and 45 m 2 / g, and more preferably between 15 m 2 / g and 40 m 2 / g. The large surface leads to a better and more uniform absorption of the electromagnetic energy, which is used for selective melting of areas of a powder layer is needed. Conversely, this means that when using powder according to the invention can be operated with lower energy, and the components show less heat input into surrounding areas due to the lower energy input and thus are more accurate. In particular, the problem of "round corners" or the growth of components in areas of high heat input is largely avoided. With prior art PAEK powders having BET surface areas of less than 1 m 2 / g, this effect is not achieved. The crystallite melting point of the powder of the invention depends on the type of PAEK used; it is above 300 ° C.
Weiterhin erfordert es die Verarbeitung in einer Rapid-Prototyping/Rapid-Manufacturing- Anlage, zwecks automatisierter Pulverzuführung, Dosierung und Auftrag einer dünnen Pulverschicht, dass die verwendeten Pulver ausreichend rieselfähig sind. Dazu empfiehlt es sich, Rieselhilfe nach dem Stand der Technik, beispielsweise pyrogenes Siliciumdioxid, beizugeben. Typische Mengen an Rieselhilfe bewegen sich zwischen 0,01 und 10 %, bezogen auf das in der Komposition enthaltene Polymer.Furthermore, it requires processing in a rapid prototyping / rapid-manufacturing plant, for the purpose of automated powder feed, metering and application of a thin layer of powder, that the powders used are sufficiently free-flowing. For this purpose, it is advisable Rieselhilfe according to the prior art, for example, pyrogenic silica, zuiggeben. Typical amounts of flow aid range between 0.01 and 10%, based on the polymer contained in the composition.
Um auf der einen Seite eine ausreichende Fließfähigkeit des selektiv durch die elektromagnetische Energie aufgeschmolzenen PAEK zu gewährleisten, damit gegebenenfalls eine Verbindung zur darunterliegenden Schicht erzielt wird und möglichst lunkerfreie Bauteile erstellt werden können, sowie auf der anderen Seite eine gute mechanische Festigkeit der Bauteile zu erreichen, liegt der bevorzugte Bereich für die Lösungsviskosität zwischen 0,2 und 1,3, besonders bevorzugt zwischen 0,5 und 1,1. Die Lösungsviskosität am PAEK wird dabei nach EN ISO 1628-1 bzw. in Anlehnung an DIN EN ISO 307 in 96%iger Schwefelsäure ermittelt. Desweiteren ist es von Vorteil, wenn das Molekulargewicht während des Verarbeitungsprozesses in einer Rapid-Prototyping/Rapid-Manufacturing-Anlage zumindest erhalten bleibt, als besonders bevorzugt ist ein Anstieg des Molekulargewichtes einzustufen.In order to ensure on the one hand sufficient flowability of the selectively melted by the electromagnetic energy PAEK, so possibly a connection to the underlying layer is achieved and possible void-free components can be created, and on the other hand to achieve a good mechanical strength of the components, For example, the preferred range for solution viscosity is between 0.2 and 1.3, more preferably between 0.5 and 1.1. The solution viscosity at the PAEK is determined in accordance with EN ISO 1628-1 or in accordance with DIN EN ISO 307 in 96% sulfuric acid. Furthermore, it is advantageous if the molecular weight is at least maintained during the processing process in a rapid prototyping / rapid-manufacturing plant, as is particularly preferred to classify an increase in molecular weight.
Eine weitere vorteilhafte Modifizierung des PAEK-Pulvers besteht in der Einarbeitung eines geeigneten Absorbers. Der Absorber kann entweder gleichmäßig im Partikel verteilt sein, sich im Inneren oder oberflächennah konzentrieren.A further advantageous modification of the PAEK powder is the incorporation of a suitable absorber. The absorber can either be evenly distributed in the particle, in the Focus inside or near the surface.
Bei dem Absorber, besonders IR-Absorber, kann es sich um Farbmittel oder andere Zusatzstoffe handeln. Beispiele dafür sind Ruß, KHP (Kupferhydroxidphosphat), Knochenkohle, Flammschutzmittel auf Basis Melamincyanurat oder Phosphor, Kohlenstofffasern, Kreide, Graphit oder für vornehmlich transparente Pulver z.B. Interferenzpigmente und ClearWeld® (WO 0238677), ohne die Erfindung darauf beschränken zu wollen. Die Modifizierung des PAEK-Pulvers kann auf die verschiedenste Art und Weise erfolgen.
Daher ist ebenso Gegenstand der vorliegenden Erfindung ein Verfahren zur Modifizierung von PAEK-Pulver , welches dadurch gekennzeichnet ist, dass entweder eine pulverförmige Mischung des erfindungsgemäßen PAEK-Pulvers und eines entsprechenden Absorbers hergestellt wird.The absorber, especially IR absorbers, may be colorants or other additives. Examples thereof are carbon black, KHP (copper hydroxide phosphate), bone char, flame retardants based on melamine cyanurate or phosphorus, carbon fibers, chalk, graphite or for predominantly transparent powders, for example interference pigments and ClearWeld® (WO 0238677), without wishing to restrict the invention to this. The modification of the PAEK powder can be done in a variety of ways.
Therefore, the present invention is also a process for the modification of PAEK powder, which is characterized in that either a powdered mixture of the PAEK powder according to the invention and a corresponding absorber is prepared.
Das erfmdungsgemäße Pulver weist bezogen auf die Summe der im Pulver vorhandenen Polymere vorzugsweise von 0,01 bis 30 Massen-% an einem Absorber, bevorzugt von 0,05 bis 20 Massen-% eines Absorbers, besonders bevorzugt von 0,2 bis 15 Massen-% eines Absorbers und ganz besonders bevorzugt von 0,4 bis 10 Massen-% eines Absorbers, auf. Die angegebenen Bereiche beziehen sich dabei auf den Gesamtgehalt eines durch elektromagnetische Energie anregbaren Absorbers im Pulver, wobei mit Pulver die gesamte aus Komponenten bestehende Menge gemeint ist.
Das erfindungsgemäße Pulver kann eine Mischung eines Absorbers und Polymerpartikeln aufweisen oder aber Polymerpartikel bzw. -pulver, welche eingearbeiteten Absorber aufweisen. Bei einem Anteil des Absorbers von unter 0,01 Massen-% bezogen auf die gesamte aus Komponenten bestehende Menge nimmt der gewünschte Effekt der verbesserten Aufschmelzbarkeit der gesamten Komposition durch elektromagnetische Wellen deutlich ab. Bei einem Anteil des Absorbers von über 30 Massen-% bezogen auf die gesamte aus Komponenten bestehende Menge verschlechtern sich die mechanischen Eigenschaften wie z.B. die Reißdehnung der aus solchen Pulvern hergestellten Formkörper deutlich und die Verarbeitbarkeit leidet.
Der Absorber weist vorzugsweise eine Partikelgröße auf, die die mittlere Korngröße d50 der Polymerpartikel bzw. -pulver um mindestens 20 %, vorzugsweise um mehr als 50 % und ganz besonders bevorzugt um mehr als 70 % unterschreiten. Insbesondere weist der Absorber eine mittlere Partikelgröße von 0,001 bis 50 µm, bevorzugt von 0,02 bis 10 µm auf. Durch die geringe Partikelgröße kommt es zu einer guten Verteilung des pulverförmigen Absorbers in dem pulverförmigen Polymerpulver.The powder according to the invention has, based on the sum of the polymers present in the powder, preferably from 0.01 to 30% by mass of an absorber, preferably from 0.05 to 20% by mass of an absorber, particularly preferably from 0.2 to 15% by mass. % of an absorber and most preferably from 0.4 to 10% by mass of an absorber. The ranges given here are based on the total content of an excitable by electromagnetic energy absorber in the powder, wherein powder is meant the entire amount consisting of components.
The powder according to the invention may comprise a mixture of an absorber and polymer particles or else polymer particles or powder having incorporated absorbers. With a proportion of the absorber of less than 0.01% by mass, based on the total amount consisting of components, the desired effect of the improved meltability of the entire composition by electromagnetic waves decreases significantly. With a proportion of the absorber of more than 30% by mass, based on the total amount consisting of components, the mechanical properties, such as, for example, the elongation at break of the shaped bodies produced from such powders, deteriorate markedly and processability suffers.
The absorber preferably has a particle size which the average particle size d 50 of the polymer particles or powder by at least 20%, preferably by more than 50% and completely more preferably below by more than 70%. In particular, the absorber has an average particle size of 0.001 to 50 microns, preferably from 0.02 to 10 microns. Due to the small particle size, there is a good distribution of the powdered absorber in the powdery polymer powder.
Im einfachsten Fall weist der Absorber ein sogenanntes Farbmittel auf. Unter einem Farbmittel versteht man alle farbgebenden Stoffe nach DIN 55944, welche in anorganische und organische Farbmittel sowie in natürliche und synthetische Farbmittel einteilbar sind (s. Römpps Chemielexikon, 1981, 8. Auflage, S 1237). Nach DIN 55943 (Sept. 1984) und DIN 55945 (Aug. 1983) ist ein Pigment ein im Anwendungsmedium praktisch unlösliches, anorganisches oder organisches, buntes oder unbuntes Farbmittel. Farbstoffe sind in Lösemitteln und/oder Bindemitteln lösliche anorganische oder organische, bunte oder unbunte Farbmittel.
Der Absorber kann aber auch seine absorbierende Wirkung dadurch erhalten, dass er Zusatzstoffe aufweist. Das können beispielsweise Flammschutzmittel auf der Basis von Melamincyanurat sein (Melapur von der DSM), oder auf der Basis von Phosphor, bevorzugt Phosphate, Phosphite, Phosphonite, oder elementarer roter Phosphor. Ebenfalls als Zusatzstoff geeignet sind Kohlenstofffasern, bevorzugt gemahlen, Glaskugeln, auch hohl, oder Kaolin, Kreide, Wollastonit, oder Graphit.In the simplest case, the absorber has a so-called colorant. A colorant is understood to mean all colorants according to DIN 55944, which can be classified into inorganic and organic colorants and into natural and synthetic colorants (see Rompps Chemie Lexikon, 1981, 8th edition, page 1237). According to DIN 55943 (Sept. 1984) and DIN 55945 (Aug. 1983), a pigment is a virtually insoluble, inorganic or organic, colored or achromatic colorant in the application medium. Dyes are soluble in solvents and / or binders inorganic or organic, colored or achromatic colorants.
The absorber can also receive its absorbing effect by having additives. These can be, for example, melamine cyanurate-based flame retardants (Melapur from the DSM) or based on phosphorus, preferably phosphates, phosphites, phosphonites, or elemental red phosphorus. Also suitable as an additive are carbon fibers, preferably ground, glass beads, also hollow, or kaolin, chalk, wollastonite, or graphite.
Der im erfindungsgemäßen Pulver enthaltene Absorber weist bevorzugt Ruß oder KHP (Kupferhydroxidphoshat) oder Kreide, Knochenkohle, Kohlenstofffasern, Graphit, Flammschutzmittel oder Interferenzpigmente als Hauptkomponente auf. Interferenzpigmente sind sogenannte Perlglanzpigmente. Auf Basis von dem natürlichen Mineral Glimmer werden sie mit einer dünnen Schicht aus Metalloxiden, zum Beispiel Titandioxid und/oder Eisenoxid umhüllt und stehen mit einer mittleren Korngrößenverteilung zwischen 1 und 60 µm zur Verfügung. Interferenzpigmente werden beispielsweise von der Fa. Merck unter dem Namen Iriodin angeboten. Die Iriodinpalette von Merck umfasst Perlglanzpigmente und metalloxidbeschichtete Glimmerpigmente sowie die Unterklassen: Interferenzpigmente, Metallglanz-Effektpigmente (Eisenoxidbeschichtung des Glimmerkerns), Silberweiß-Effektpigmente, Goldglanzeffektpigmente(mit Titandioxid und Eisenoxid beschichteter Glimmerkern). Besonders bevorzugt ist die Verwendung von Iriodintypen der Iriodin-LS-Reihe, namentlich Iriodin LS 820, Iriodin LS 825, Iriodin LS 830, Iriodin LS 835 und Iriodin LS 850. Ganz besonders bevorzugt ist die Verwendung von Iriodin LS 820 und Iriodin LS 825.The absorber contained in the powder according to the invention preferably has carbon black or KHP (Kupferhydroxidphoshat) or chalk, bone charcoal, carbon fibers, graphite, flame retardants or interference pigments as the main component. Interference pigments are so-called pearlescent pigments. Based on the natural mineral mica, they are coated with a thin layer of metal oxides, for example titanium dioxide and / or iron oxide, and are available with a mean particle size distribution between 1 and 60 μm. Interference pigments are offered for example by Merck under the name Iriodin. The Iriodin range from Merck includes pearlescent pigments and metal-oxide-coated mica pigments as well as the subclasses: interference pigments, metallic luster effect pigments (iron oxide coating of the mica core), silver-white effect pigments, Gold gloss effect pigments (titanium oxide and iron oxide coated mica core). Particularly preferred is the use of iriodin types of the Iriodin LS series, namely Iriodin LS 820, Iriodin LS 825, Iriodin LS 830, Iriodin LS 835 and Iriodin LS 850. Very particular preference is given to the use of Iriodin LS 820 and Iriodin LS 825.
Daneben eignen sich ebenfalls: Glimmer bzw. Glimmerpigmente, Titandioxid, Kaolin, organische und anorganische Farbpigmente, Antimon(III)oxid, Metallpigmente, Pigmente auf der Basis von Bismutoxichlorid (z. B. Serie Biflair von Merck, Hochglanzpigment), Indiumzinnoxid (Nano ITO-Pulver, von Nanogate Technologies GmbH oder AdNanotm ITO der Degussa), AdNanotm Zinkoxid (Degussa), Lantanhexachlorid, ClearWeld® (WO 0238677) sowie kommerziell erhältliche Flammschutzmittel, welche Melamincyanurat oder Phosphor, bevorzugt Phosphate, Phosphite, Phosphonite oder elementaren (roter) Phosphor, aufweisen.Also suitable are: mica or mica pigments, titanium dioxide, kaolin, organic and inorganic color pigments, antimony (III) oxide, metal pigments, pigments based on bismuth oxychloride (eg Merck series Biflair, high gloss pigment), indium tin oxide (Nano ITO Powder, from Nanogate Technologies GmbH or AdNano tm ITO of Degussa), AdNano tm zinc oxide (Degussa), lanthanum hexachloride, ClearWeld® (WO 0238677) and commercially available flame retardants which melamine cyanurate or phosphorus, preferably phosphates, phosphites, phosphonites or elemental (red ) Phosphorus.
Wenn eine Störung der Eigenfarbe des Pulvers vermieden werden soll, weist der Absorber bevorzugt Interferenzpigmente, besonders bevorzugt aus der Iriodin LS-Reihe von Merck, oder Clearweld®, aus.If a disturbance of the intrinsic color of the powder is to be avoided, the absorber preferably exhibits interference pigments, particularly preferably from the Iriodin LS series from Merck, or Clearweld®.
Die chemische Bezeichnung für das KHP ist Kupferhydroxidphosphat; dieses wird als hellgrünes, feines kristallines Pulver mit einem mittleren Korndurchmesser von knapp 3 µm eingesetzt.The chemical name for the KHP is copper hydroxide phosphate; This is used as a light green, fine crystalline powder with a mean grain diameter of almost 3 microns.
Der Ruß kann nach dem Furnacerußverfahren, dem Gasrußverfahren oder dem Flammrußverfahren hergestellt werden, vorzugsweise nach dem Furnacerußverfahren. Die Primärteilchengröße liegt zwischen 10 und 100 nm, vorzugsweise zwischen 20 und 60 nm, die Kornverteilung kann eng oder breit sein. Die BET-Oberfläche nach DIN 53601 liegt zwischen 10 und 600 m2/g, bevorzugt zwischen 70 und 400 m2/g. Die Rußpartikel können zur Einstellung von Oberflächenfunktionalitäten oxidativ nachbehandelt sein. Sie können hydrophob (beispielsweise Printex 55 oder Flammruß 101 der Degussa) oder hydrophil (beispielsweise Farbruß FW20 oder Printex 150 T der Degussa) eingestellt sein. Sie können hochstrukturiert oder niederstrukturiert sein; damit wird ein Aggregationsgrad der Primärteilchen beschrieben. Durch die Verwendung spezieller Leitfähigkeitsruße kann die elektrische Leitfähigkeit der aus dem erfindungsgemäßen Pulver hergestellten Bauteile eingestellt werden. Durch die Verwendung von geperlten Rußen kann eine bessere Dispergierbarkeit sowohl bei den nassen als auch bei den trockenen Mischverfahren genutzt werden. Auch die Verwendung von Rußdispersionen kann von Vorteil sein.The carbon black can be produced by the furnace black process, the gas black process, or the flame black process, preferably by the furnace black process. The primary particle size is between 10 and 100 nm, preferably between 20 and 60 nm, the grain distribution can be narrow or wide. The BET surface area according to DIN 53601 is between 10 and 600 m 2 / g, preferably between 70 and 400 m 2 / g. The soot particles can be oxidatively treated to adjust surface functionalities. They may be hydrophobic (for example Printex 55 or Flegruß 101 from Degussa) or hydrophilic (for example carbon black FW20 or Printex 150 T from Degussa). They can be highly structured or low-structured; This describes a degree of aggregation of the primary particles. By use special conductivity carbon black, the electrical conductivity of the components produced from the powder according to the invention can be adjusted. The use of beaded carbon blacks allows better dispersibility in both wet and dry mixing processes. The use of carbon black dispersions may also be advantageous.
Knochenkohle ist ein mineralisches Schwarzpigment, welches elementaren Kohlenstoff enthält. Sie besteht zu 70 bis 90 % aus Calciumphosphat und zu 30 bis 10 % aus Kohlenstoff. Die Dichte liegt typischerweise zwischen 2,3 und 2,8 g/ml.Bone charcoal is a mineral black pigment that contains elemental carbon. It consists of 70 to 90% calcium phosphate and 30 to 10% carbon. The density is typically between 2.3 and 2.8 g / ml.
Der Absorber kann auch eine Mischung von organischen und/oder anorganischen Pigmenten, Flammschutzmitteln, oder anderen Farbmitteln enthalten, die jedes für sich elektromagnetische Wellen schlecht absorbieren, in der Kombination jedoch ausreichend gut zur Verwendung im erfindungsgemäßen Verfahren die eingetragene elektromagnetische Energie absorbieren.
Der Absorber kann beispielsweise als Granulat, oder als Pulver vorliegen. Je nach Herstellverfahren des für das erfindungsgemäße Verfahren geeigneten Pulvers können sie vermahlen oder nachgemahlen werden. Falls die Verwendung einer Dispersion für das Herstellverfahren von Vorteil ist, so kann der Absorber entweder bereits als Dispersion vorliegen, oder aus feinteiligen Absorberpartikeln eine Dispersion hergestellt werden. Der Absorber kann auch als Flüssigkeit vorliegen. Als Beispiel hierfür sei ClearWeld® genannt.
Solche Additive, die hier als Absorber verwendet werden, sind beispielsweise bei der Firma Merck unter dem Namen Iriodin® erhältlich. Mit Ruß sind handelsübliche Standardruße gemeint, wie sie beispielsweise von den Firmen Degussa AG, Cabot Corp., oder Continental Carbon angeboten werden.The absorber may also contain a mixture of organic and / or inorganic pigments, flame retardants, or other colorants which poorly absorb any electromagnetic waves of their own but, in combination, absorb the registered electromagnetic energy sufficiently well for use in the process of the present invention.
The absorber can be present, for example, as granules or as a powder. Depending on the method of preparation of the powder suitable for the process according to the invention, they can be ground or reground. If the use of a dispersion is advantageous for the preparation process, the absorber can either already be in the form of a dispersion or a dispersion can be prepared from finely divided absorbent particles. The absorber can also be present as a liquid. An example of this is ClearWeld®.
Such additives, which are used here as absorbers, are available, for example, from Merck under the name Iriodin®. By carbon black are meant commercially available standard blacks, such as those offered by the companies Degussa AG, Cabot Corp., or Continental Carbon.
Kommerziell erhältliche Beispiele für geeignete Absorber im allgemeinen sind Iriodin® LS 820 oder Iriodin® LS 825 oder Iriodin® LS 850 der Firma Merck. Als Beispiel für den Ruß mag Printex 60, Printex A, Printex XE2, oder Printex Alpha der Firma Degussa dienen. Geeignetes KHP wird ebenfalls von der Firma Degussa unter dem Markennamen Vestodur FP-LAS angeboten.Commercially available examples of suitable absorbers in general are Iriodin® LS 820 or Iriodin® LS 825 or Iriodin® LS 850 from Merck. An example of the carbon black may be Printex 60, Printex A, Printex XE2, or Printex Alpha from Degussa. Suitable KHP is also offered by Degussa under the brand name Vestodur FP-LAS.
Erfindungsgemäßes Pulver kann außerdem zumindest einen Hilfsstoff, zumindest einen Füllstoff und/oder zumindest ein Pigment aufweisen. Solche Hilfsstoffe können z.B. Rieselhilfsmittel, wie z.B. pyrogenes Siliziumdioxid oder auch gefällte Kieselsäure sein. Pyrogenes Siliziumdioxid (pyrogene Kieselsäure) wird zum Beispiel unter dem Produktnamen Aerosil®, mit unterschiedlichen Spezifikationen, durch die Degussa AG angeboten. Vorzugsweise weist erfindungsgemäßes Pulver weniger als 3 Massen-%, vorzugsweise von 0,001 bis 2 Massen-% und ganz besonders bevorzugt von 0,05 bis 1 Massen-% solcher Pigmente bezogen auf Gesamtsumme der Komponenten, also der Summe aus Polymeren und Absorber auf. Die Füllstoffe können z.B. Glas-, Metall-, insbesondere Aluminium- oder Keramikpartikel, wie z.B. massive oder hohle Glaskugeln, Stahlkugeln, Aluminiumkugeln oder Metallgrieß oder auch Buntpigmente, wie z.B. Übergangsmetalloxide sein.Powder according to the invention may also comprise at least one adjuvant, at least one filler and / or at least one pigment. Such adjuvants may be e.g. Flow aids, such as be fumed silica or precipitated silica. Pyrogenic silica (fumed silica) is offered by Degussa AG, for example, under the product name Aerosil®, with different specifications. Preferably, powder according to the invention has less than 3% by mass, preferably from 0.001 to 2% by mass and very particularly preferably from 0.05 to 1% by mass of such pigments, based on the total sum of the components, ie the sum of polymers and absorbers. The fillers may e.g. Glass, metal, especially aluminum or ceramic particles, e.g. solid or hollow glass beads, steel balls, aluminum balls or metal grit or even colored pigments, such as e.g. Be transition metal oxides.
Die Füllstoffpartikel weisen dabei vorzugsweise eine kleinere oder ungefähr gleich große mittlere Korngröße wie die Partikel der Polymere oder die mit Polymer umhüllten Partikel auf. Vorzugsweise sollte die mittlere Korngröße d50 der Füllstoffe die mittlere Korngröße d50 der Polymere um nicht mehr als 20 %, vorzugsweise um nicht mehr als 15 % und ganz besonders bevorzugt um nicht mehr als 5 % unterschreiten. Die Partikelgröße ist insbesondere limitiert durch die zulässige Bauhöhe bzw. Schichtdicke in der jeweils verwendeten schichtweise arbeitenden Apparatur.The filler particles preferably have a smaller or approximately the same size as the average particle size of the particles of the polymers or the particles coated with polymer. The average particle size d 50 of the fillers should preferably not fall below the mean particle size d 50 of the polymers by more than 20%, preferably by not more than 15%, and very particularly preferably by not more than 5%. The particle size is in particular limited by the permissible construction height or layer thickness in the layered apparatus used in each case.
Vorzugsweise weist erfindungsgemäßes Pulver weniger als 75 Massen-%, bevorzugt von 0,001 bis 70 Massen-%, besonders bevorzugt von 0,05 bis 50 Massen-% und ganz besonders bevorzugt von 0,5 bis 25 Massen-% solcher Füllstoffe bezogen auf die Gesamtsumme der Komponenten auf, so dass der Volumenanteil der Polymere in jedem Fall größer 50 % beträgt. Falls es sich um gecoatete Partikel handelt, kann der Volumenanteil der Polymere auch kleiner als 50 % sein.
Beim Überschreiten der angegebenen Höchstgrenzen für Hilfs- und/oder Füllstoffe kann es, je nach eingesetztem Füll- oder Hilfsstoff zu deutlichen Verschlechterungen der mechanischen Eigenschaften von Formkörpern kommen, die mittels solcher Pulver hergestellt wurden.Preferably, powder according to the invention has less than 75% by mass, preferably from 0.001 to 70% by mass, more preferably from 0.05 to 50% by mass and most preferably from 0.5 to 25% by mass of such fillers, based on the total of the components, so that the volume fraction of the polymers in each case is greater than 50%. In the case of coated particles, the volume fraction of the polymers may also be less than 50%.
Exceeding the specified maximum limits for auxiliaries and / or fillers, depending on the filler or auxiliary used, can lead to significant deterioration of the mechanical properties of moldings produced by means of such powders.
Die Herstellung der erfindungsgemäßen Pulver ist einfach möglich und erfolgt bevorzugt gemäß dem erfindungsgemäßen Verfahren zur Herstellung von erfindungsgemäßem Pulver, welches sich dadurch auszeichnet, dass ein PAEK-Pulver hergestellt wird, gegebenenfalls die entstandene Kornfraktion oder Kornform für den Einsatz im RP/RM-Verfahren angepaßt wird, weiterhin gegebenenfalls anschließend mit Hilfs- und Zusatzstoffen versehen wird, und im Bedarfsfalle mit einem Absorber versetzt wird. Die optimale Reihenfolge der auf das Basismaterial angewandten Modifikationen soll durch die Aufzählung nicht vorweggenommen sein. Die Hilfs- und Zusatzstoffe bzw. der Absorber können im Dry Blend eingebracht werden.
Dabei kann es von Vorteil sein, bei der Verwendung eines pulverförmigen Absorbers den Absorber zunächst allein oder aber auch die fertige Mischung mit einer Rieselhilfe zu versehen, beispielsweise aus der Aerosil-Reihe von Degussa, z. B. Aerosil R972 oder R812 oder Aerosil 200.The preparation of the powders according to the invention is easily possible and is preferably carried out according to the inventive method for producing powder according to the invention, which is characterized in that a PAEK powder is prepared, optionally, the resulting grain fraction or grain shape is adapted for use in the RP / RM process, further optionally provided subsequently with auxiliaries and additives , And in case of need with an absorber is added. The optimal order of the modifications applied to the base material should not be anticipated by the list. The auxiliaries and additives or the absorber can be incorporated in the dry blend.
It may be advantageous to provide the absorber first alone or else the finished mixture with a flow aid when using a powdered absorber, for example from the Aerosil series of Degussa, z. As Aerosil R972 or R812 or Aerosil 200th
Das Pulver kann bei dieser Variante des erfindungsgemäßen Verfahrens ein bereits für Rapid-Prototyping/Rapid-Manufacturing-Verfahren geeignetes PAEK-Pulver sein, dem einfach feinteilige Partikel des Absorbers zugemischt werden. Die Partikel weisen dabei vorzugsweise eine kleinere bis maximal ungefähr gleich große mittlere Korngröße wie die Polymer aufweisenden Partikel auf. Vorzugsweise sollte die mittlere Korngröße d50 des Absorbers die mittlere Korngröße d50 der Polymerpulver um mehr als 20 %, vorzugsweise um mehr als 50 % und ganz besonders bevorzugt um mehr als 70 % unterschreiten. Die Korngröße ist nach oben hin insbesondere limitiert durch die zulässige Bauhöhe bzw. Schichtdicke in der Rapid-Prototyping/Rapid-Manufacturing-Anlage. Insbesondere weist der Absorber eine mittlere Partikelgröße von 0,001 bis 50 µm, bevorzugt von 0,02 bis 10 µm auf.In this variant of the method according to the invention, the powder may be a PAEK powder which is already suitable for rapid prototyping / rapid-manufacturing processes and to which finely divided particles of the absorber are simply added. In this case, the particles preferably have a smaller to at most approximately equal size average particle size than the polymer-comprising particles. The average particle size d 50 of the absorber should preferably be below the mean particle size d 50 of the polymer powders by more than 20%, preferably by more than 50% and very particularly preferably by more than 70%. The grain size is limited to the top in particular by the allowable height or layer thickness in the rapid prototyping / rapid-manufacturing plant. In particular, the absorber has an average particle size of 0.001 to 50 microns, preferably from 0.02 to 10 microns.
Insbesondere durch die Verwendung von PAEK-Pulvern, welche sich durch eine hohe BET-Oberfläche auszeichnen, ist eine sehr gute Verteilung des Absorbers gegeben. Aus eigenen Untersuchungen ist bekannt, dass Pigmente, die auf einer relativ glatten Oberfläche von Partikeln mit einer BET-Oberfläche unterhalb von 1 m2/g verteilt sind, zu einem starken Abfall der mechanischen Eigenschaften an den damit hergestellten Bauteilen führen. Insbesondere die Reißdehnung leidet unter den Sollbruchstellen, die die Pigmentkonzentration auf der Oberfläche darstellt. Überraschenderweise wurde nun gefunden, dass die hohe BET-Oberfläche zu einer guten Verteilung des Absorbers führt, und dass damit Bauteile mit höherer Dichte und besseren mechanischen Eigenschaften, insbesondere Reißdehnung, hergestellt werden können wenn erfindungsgemäßes PAEK-Pulver in einem der weiter oben beschriebenen Verfahren verwendet wird.In particular, by the use of PAEK powders, which are characterized by a high BET surface area, a very good distribution of the absorber is given. From our own investigations it is known that pigments, which are distributed on a relatively smooth surface of particles with a BET surface area below 1 m 2 / g, lead to a sharp decrease in the mechanical properties of the components produced therewith. In particular, the elongation at break suffers from the predetermined breaking points, which represents the pigment concentration on the surface. Surprisingly, it has now been found that the high BET surface area to a good Distribution of the absorber leads, and that thus components with higher density and better mechanical properties, in particular elongation at break, can be produced when inventive PAEK powder is used in one of the methods described above.
Gegebenenfalls kann zur Verbesserung des Rieselverhaltens dem erfindungsgemäßen Pulver eine geeignete Rieselhilfe, wie pyrogenes Aluminiumoxid, pyrogenes Siliziumdioxid oder pyrogenes Titandioxid, dem gefällten oder gemahlenen Pulver äußerlich zugesetzt werden.Optionally, a suitable flow aid, such as pyrogenic alumina, fumed silica or pyrogenic titanium dioxide, the precipitated or ground powder may be added externally to the powder of the invention to improve the trickle.
Eine feinteilige Vermischung kann in der einfachsten Ausführungsart des erfindungsgemäßen Verfahrens beispielsweise durch Aufmischen fein gepulverten Absorbers auf das trockene Pulver in schnelllaufenden mechanischen Mischern erfolgen.A finely divided mixing can be carried out in the simplest embodiment of the method according to the invention, for example by mixing finely powdered absorber on the dry powder in high-speed mechanical mixers.
Als Absorber können handelsübliche Produkte, die beispielsweise bei der Fa. Merck oder Degussa unter dem Handelsnamen Iriodin® oder Printex® bezogen werden können, bzw. die oben beschriebenen eingesetzt werden.Commercially available products which can be obtained, for example, from Merck or Degussa under the trade name Iriodin® or Printex®, or those described above, can be used as absorbers.
Zur Verbesserung der Verarbeitungsfähigkeit oder zur weiteren Modifikation des Pulvers können diesem anorganische Pigmente, insbesondere Buntpigmente, wie z.B. Übergangsmetalloxide, Stabilisatoren, wie z.B. Phenole, insbesondere sterisch gehinderte Phenole, Verlaufs- und Rieselhilfsmittel, wie z.B. pyrogene Kieselsäuren sowie Füllstoffpartikel zugegeben werden. Vorzugsweise wird, bezogen auf das Gesamtgewicht an Komponenten im Pulver, soviel dieser Stoffe den Pulvern zugegeben, dass die für das erfindungsgemäße Pulver angegeben Konzentrationen für Füll- und/oder Hilfsstoffe eingehalten werden.To improve the processability or to further modify the powder, inorganic pigments, in particular colored pigments, such as e.g. Transition metal oxides, stabilizers, e.g. Phenols, in particular sterically hindered phenols, flow and flow aids, such. fumed silicas and filler particles are added. Preferably, based on the total weight of components in the powder, so much of these substances are added to the powders that the concentrations for fillers and / or auxiliaries stated for the powder according to the invention are maintained.
Außerdem kann es vorteilhaft sein, wenn als Pulver eine Mischung hergestellt wird, die neben den PAEK-Partikeln auch diverse Füllstoffe wie z. B. Glaspartikel, Keramikpartikel oder Metallpartikel aufweisen, oder weitere Additive wie beispielsweise Flammschutzmittel. Typische Füllstoffe sind z. B. Metallgrieße, beispielsweise Alugrieß, oder Stahl- oder Glaskugeln.In addition, it may be advantageous if a mixture is prepared as a powder, in addition to the PAEK particles and various fillers such. As glass particles, ceramic particles or metal particles, or other additives such as flame retardants. Typical fillers are z. B. Metallgrieße, for example Alugrieß, or steel or glass beads.
Die Füllstoffpartikel weisen dabei vorzugsweise eine kleinere oder ungefähr gleich große mittlere Partikelgröße wie die PAEK aufweisenden Partikel auf. Vorzugsweise sollte die mittlere Partikelgröße d50 der Füllstoffe die mittlere Partikelgröße d50 der PAEK aufweisenden Partikel um nicht mehr als 20 %, vorzugsweise um nicht mehr als 15 % und ganz besonders bevorzugt um nicht mehr als 5 % überschreiten. Die Partikelgröße ist insbesondere limitiert durch die zulässige Bauhöhe bzw. Schichtdicke in einer wie für oben beschriebene Verfahren (RP/RM-Verfahren) geeignete RP/RM-Apparatur. Typischerweise werden Glaskugeln mit einem mittleren Durchmesser von 20 bis 80 µm verwendet. Ein weiterer Vorzugsbereich sind liegt bei durchschnittlichen Partikelgrößen für die Füllstoffe bzw. Additive unterhalb von 20 µm, bevorzugt unterhalb 15 µm.The filler particles in this case preferably have a smaller or approximately the same size as the average particle size of the PAEK-comprising particles. Preferably, the average particle size d 50 of the fillers should not exceed the average particle size d 50 of the PAEK-containing particles by more than 20%, preferably by not more than 15% and most preferably by not more than 5%. In particular, the particle size is limited by the permissible structural height or layer thickness in a RP / RM apparatus suitable for the method described above (RP / RM method). Typically, glass spheres with a mean diameter of 20 to 80 microns are used. Another preferred range is average particle sizes for the fillers or additives below 20 microns, preferably below 15 microns.
Gegenstand der vorliegenden Erfindung ist auch die Verwendung von erfindungsgemäßem Pulver zur Herstellung von Formkörpern in einem schichtweise arbeitenden und selektiv das Pulver aufschmelzenden (Rapid-Prototyping- oder Rapid-Manufacturing-) Verfahren, bei denen erfindungsgemäße Pulver, die zusätzlich wie beschrieben modifiziert sein können und/oder einen Absorber aufweisen können, eingesetzt werden.The present invention also provides the use of inventive powder for the production of moldings in a layer-by-layer and selectively melting the powder (rapid prototyping or rapid-manufacturing) method, in which powders according to the invention, which may additionally be modified as described, and / or have an absorber can be used.
Insbesondere ist Gegenstand der vorliegenden Erfindung die Verwendung des erfindungsgemäßen PAEK-Pulvers, welches zusätzlich wie beschrieben modifiziert sein kann und/oder einen Absorber aufweisen kann, zur Herstellung von Formkörpern durch selektives Lasersintern.In particular, the present invention is the use of the PAEK powder according to the invention, which may additionally be modified as described and / or may have an absorber for the production of moldings by selective laser sintering.
Die Laser-Sinter-Verfahren sind hinlänglich bekannt und beruhen auf dem selektiven Sintern von Polymerpartikeln, wobei Schichten von Polymerpartikeln kurz einem Laserlicht ausgesetzt werden und so die Polymerpartikel, die dem Laserlicht ausgesetzt waren, verschmolzen werden. Durch die aufeinanderfolgende Versinterung von Schichten von Polymerpartikeln werden dreidimensionale Objekte hergestellt. Einzelheiten zum Verfahren des selektiven Laser-Sinterns sind z.B. den Schriften US 6,136,948 und WO 96/06881 zu entnehmen. Die Wellenlänge des üblicherweise verwendeten CO2-Lasers beträgt dabei 10600 nm. Das erfmdungsgemäße Pulver kann, insbesondere wenn es einen Absorber aufweist, aber auch in Verfahren, welches Laser mit einer Wellenlänge zwischen 100 und 3000 nm, bevorzugt zwischen 800 und 1070 nm oder zwischen 1900 und 2100 nm, verwendet, insbesondere in dem oben beschriebenen, eingesetzt werden. So kann das erfindungsgemäße Pulver insbesondere zur Herstellung von Formkörpern aus Pulvern durch das SLS-Verfahren (selektives Lasersintern) mittels Lasern mit einer Wellenlänge von 10600 nm, und zwischen 100 und 3000 nm, bevorzugt zwischen 800 und 1070 nm oder zwischen 1900 und 2100 nm, verwendet werden.The laser-sintering processes are well known and rely on the selective sintering of polymer particles whereby layers of polymer particles are briefly exposed to laser light, thus fusing the polymer particles exposed to the laser light. The successive sintering of layers of polymer particles produces three-dimensional objects. Details of the method of selective laser sintering can be found, for example, in the specifications US Pat. No. 6,136,948 and WO 96/06881. The wavelength of the commonly used CO 2 laser is 10600 nm. The erfmdungsgemäße powder, in particular if it has an absorber, but also in processes which laser with a wavelength between 100 and 3000 nm, preferably between 800 and 1070 nm or between 1900 and 2100 nm, used, in particular in that described above. Thus, the powder according to the invention can be used in particular for the production of shaped bodies from powders by the SLS method (laser selective sintering) by means of lasers with a wavelength of 10600 nm, and between 100 and 3000 nm, preferably between 800 and 1070 nm or between 1900 and 2100 nm, be used.
Laserenergie mit Wellenlängen zwischen 100 und 3000 nm kann meist problemlos in einen Lichtwellenleiter eingekoppelt werden. Das ermöglicht den Verzicht auf aufwendige Spiegelsysteme, wenn dieser Lichtwellenleiter dann flexibel über das Baufeld geführt werden kann. Eine weitere Bündelung des Laserstrahls kann über Linsen oder Spiegel erfolgen. Auch eine Kühlung des Lasers ist nicht in allen Fällen erforderlich.Laser energy with wavelengths between 100 and 3000 nm can usually be easily coupled into an optical waveguide. This eliminates the need for sophisticated mirror systems, if this optical fiber can then be performed flexibly over the site. Further bundling of the laser beam can take place via lenses or mirrors. Also, a cooling of the laser is not required in all cases.
Zur Vermeidung von Curl, das bedeutet ein Aufrollen der aufgeschmolzenen Bereiche aus der Bauebene heraus, ist es sinnvoll, den Bauraum zu heizen. Bevorzugt wird auf eine Temperatur knapp unterhalb der Schmelzetemperatur des Polymeren aufgeheizt. Die Verarbeitungsparameter können durch entsprechende Vorversuche je nach Verfahren leicht herausgefunden werden. Für die erfindungsgemäßen PAEK-Pulver ist es vorteilhaft, die zum Aufschmelzen benötigte Energie schonend einzubringen.To avoid curl, which means rolling up the melted areas out of the building level, it makes sense to heat the building space. Preference is given to heating to a temperature just below the melt temperature of the polymer. The processing parameters can be easily found by appropriate preliminary tests depending on the method. For the PAEK powders according to the invention, it is advantageous to gently introduce the energy required for melting.
Die erfindungsgemäßen Formkörper, hergestellt durch ein Verfahren zum schichtweisen Aufbau von dreidimensionalen Gegenständen, bei dem selektiv Bereiche einer Pulverschicht, insbesondere des erfindungsgemäßen Pulvers, durch die Einwirkung elektromagnetischer Wellen aufgeschmolzen werden, wie z.B. dem selektiven Laser-Sintern, zeichnen sich dadurch aus, dass sie PAEK aufweisen. Besonders bevorzugt weisen sie ein PEEK, PEK, PEKK, oder ein PEEKK auf.The shaped bodies according to the invention, produced by a process for the layered construction of three-dimensional objects, in which areas of a powder layer, in particular of the powder according to the invention, are selectively melted by the action of electromagnetic waves, e.g. Selective laser sintering, characterized in that they have PAEK. Particularly preferably, they have a PEEK, PEK, PEKK, or a PEEKK.
Der gegebenenfalls im erfindungsgemäßen Formkörper vorhandene Absorber kann beispielsweise ein sogenanntes Farbmittel aufweisen. Unter einem Farbmittel versteht man alle farbgebenden Stoffe nach DIN 55944, welche in anorganische und organische Farbmittel sowie in natürliche und synthetische Farbmittel einteilbar sind (s. Römpps Chemielexikon, 1981, 8. Auflage, S 1237). Nach DIN 55943 (Sept. 1984) und DIN 55945 (Aug. 1983) ist ein Pigment ein im Anwendungsmedium praktisch unlösliches, anorganisches oder organisches, buntes oder unbuntes Farbmittel. Farbstoffe sind in Lösemitteln und/oder Bindemitteln lösliche anorganische oder organische, bunte oder unbunte Farbmittel.The absorber optionally present in the shaped article according to the invention may have, for example, a so-called colorant. A colorant is understood to mean all colorants according to DIN 55944, which can be classified into inorganic and organic colorants and into natural and synthetic colorants (see Rompps Chemielexikon, 1981, 8th edition, page 1237). To DIN 55943 (Sept. 1984) and DIN 55945 (Aug. 1983) is a pigment which is virtually insoluble in the application medium, inorganic or organic, colored or achromatic colorant. Dyes are soluble in solvents and / or binders inorganic or organic, colored or achromatic colorants.
Der im erfindungsgemäßen Formkörper gegebenenfalls vorhandene Absorber kann aber auch seine absorbierende Wirkung dadurch erhalten, dass er Zusatzstoffe aufweist. Das können beispielsweise Flammschutzmittel auf der Basis von Melamincyanurat sein (Melapur von der DSM), oder auf der Basis von Phosphor, bevorzugt Phosphate, Phosphite, Phosphonite, oder elementarer roter Phosphor. Ebenfalls als Zusatzstoff geeignet sind Kohlenstofffasern, bevorzugt gemahlen, Glaskugeln, auch hohl, oder Kaolin, Kreide, Wollastonit, oder Graphit.However, the absorber optionally present in the shaped body according to the invention can also obtain its absorbing effect by having additives. These may be, for example, melamine cyanurate based flame retardants (Melapur from the DSM) or based on phosphorus, preferably phosphates, phosphites, phosphonites or elemental red phosphorus. Also suitable as an additive are carbon fibers, preferably ground, glass beads, also hollow, or kaolin, chalk, wollastonite, or graphite.
Der gegebenenfalls im erfindungsgemäßen Formkörper vorhandene Absorber weist bevorzugt Ruß oder KHP (Kupferhydroxidphoshat) oder Kreide, Knochenkohle, Kohlenstofffasern, Graphit, Flammschutzmittel oder Interferenzpigmente als Hauptkomponente auf. Interferenzpigmente sind sogenannte Perlglanzpigmente. Auf Basis von dem natürlichen Mineral Glimmer werden sie mit einer dünnen Schicht aus Metalloxiden, zum Beispiel Titandioxid und/oder Eisenoxid umhüllt und stehen mit einer mittleren Korngrößenverteilung zwischen 1 und 60 µm zur Verfügung. Interferenzpigmente werden beispielsweise von der Fa. Merck unter dem Namen Iriodin angeboten. Die Iriodinpalette von Merck umfasst Perlglanzpigmente und metalloxidbeschichtete Glimmerpigmente sowie die Unterklassen: Interferenzpigmente, Metallglanz-Effektpigmente (Eisenoxidbeschichtung des Glimmerkerns), Silberweiß-Effektpigmente, Goldglanzeffektpigmente (mit Titandioxid und Eisenoxid beschichteter Glimmerkern). Besonders bevorzugt ist die Verwendung von Iriodintypen der Iriodin-LS-Reihe, namentlich Iriodin LS 820, Iriodin LS 825, Iriodin LS 830, Iriodin LS 835 und Iriodin LS 850. Ganz besonders bevorzugt ist die Verwendung von Iriodin LS 820 und Iriodin LS 825.The absorber optionally present in the shaped article according to the invention preferably comprises carbon black or KHP (copper hydroxide phosphate) or chalk, bone charcoal, carbon fibers, graphite, flame retardants or interference pigments as the main component. Interference pigments are so-called pearlescent pigments. Based on the natural mineral mica, they are coated with a thin layer of metal oxides, for example titanium dioxide and / or iron oxide, and are available with a mean particle size distribution between 1 and 60 μm. Interference pigments are offered for example by Merck under the name Iriodin. The Iriodin range from Merck includes pearlescent pigments and metal oxide-coated mica pigments as well as the subclasses: interference pigments, metallic luster effect pigments (iron oxide coating of the mica core), silver-white effect pigments, gold-luster effect pigments (mica core coated with titanium dioxide and iron oxide). Particularly preferred is the use of iriodin types of the Iriodin LS series, namely Iriodin LS 820, Iriodin LS 825, Iriodin LS 830, Iriodin LS 835 and Iriodin LS 850. Very particular preference is given to the use of Iriodin LS 820 and Iriodin LS 825.
Der im erfmdungsgemäßen Formkörper gegebenenfalls vorhandene Absorber kann beispielsweise Glimmer bzw. Glimmerpigmente, Titandioxid, Kaolin, organische und anorganische Farbpigmente, Antimon(111)oxid, Metallpigmente, Pigmente auf der Basis von Bismutoxichlorid (z. B. Serie Biflair von Merck, Hochglanzpigment), Indiumzinnoxid (Nano ITO-Pulver, von Nanogate Technologies GmbH oder AdNanotm ITO der Degussa), AdNanotm Zinkoxid (Degussa), Lantanhexachlorid, ClearWeld® (WO 0238677) sowie kommerziell erhältliche Flammschutzmittel, welche Melamincyanurat oder Phosphor, bevorzugt Phosphate, Phosphite, Phosphonite oder elementaren (roter) Phosphor, aufweisen.The absorber optionally present in the shaped article according to the invention can be, for example, mica or mica pigments, titanium dioxide, kaolin, organic and inorganic color pigments, Antimony (111) oxide, metal pigments, bismuth oxychloride-based pigments (eg Merck's Biflair series, high gloss pigment), indium tin oxide (Nano ITO powder, from Nanogate Technologies GmbH or AdNano tm ITO of Degussa), AdNano tm zinc oxide ( Degussa), lanthanum hexachloride, ClearWeld® (WO 0238677) and commercially available flame retardants which melamine cyanurate or phosphorus, preferably phosphates, phosphites, phosphonites or elemental (red) phosphorus.
Vorzugsweise weist der erfindungsgemäße Formkörper, bezogen auf die Summe der im Formkörper vorhandenen Komponenten, von 0,01 bis 30 Massen-% an Absorber, bevorzugt von 0,05 bis 20 Massen-%, besonders bevorzugt von 0,2 bis 15 Massen-% und ganz besonders bevorzugt von 0,4 bis 10 Massen-% auf. Maximal beträgt der Anteil an Absorber 50 Massen-% bezogen auf die Summe der im Formkörper vorhandenen Komponenten.The shaped body according to the invention, based on the sum of the components present in the shaped body, preferably has from 0.01 to 30% by mass of absorber, preferably from 0.05 to 20% by mass, particularly preferably from 0.2 to 15% by mass. and most preferably from 0.4 to 10% by mass. The maximum amount of absorber is 50% by mass, based on the sum of the components present in the molding.
Die Formkörper können neben Polymer und Absorber außerdem Füllstoffe und/oder Hilfsstoffe und/oder Pigmente, wie z.B. thermische Stabilisatoren und/oder Oxidationsstabilisatoren wie z.B. sterisch gehinderte Phenolderivate aufweisen. Füllstoffe können z.B. Glas-, Keramikpartikel und auch Metallpartikel wie zum Beispiel Eisenkugeln, bzw. entsprechende Hohlkugeln sein. Bevorzugt weisen die erfindungsgemäßen Formkörper Glaspartikel, ganz besonders bevorzugt Glaskugeln auf. Vorzugsweise weisen erfindungsgemäße Formkörper weniger als 3 Gew.-%, vorzugsweise von 0,001 bis 2 Massen-% und ganz besonders bevorzugt von 0,05 bis 1 Massen-% solcher Hilfsstoffe bezogen auf die Summe der vorhandenen Komponenten auf. Ebenso bevorzugt weisen erfmdungsgemäße Formkörper weniger als 75 Massen-%, bevorzugt von 0,001 bis 70 Massen-%, besonders bevorzugt von 0,05 bis 50 Massen-% und ganz besonders bevorzugt von 0,5 bis 25 Massen-% solcher Füllstoffe bezogen auf die Summe der vorhandenen Komponenten auf.In addition to the polymer and the absorber, the shaped articles can also contain fillers and / or auxiliaries and / or pigments, such as, for example, thermal stabilizers and / or oxidation stabilizers, e.g. have sterically hindered phenol derivatives. Fillers may e.g. Glass, ceramic particles and metal particles such as iron balls, or corresponding hollow balls be. The shaped bodies according to the invention preferably have glass particles, very particularly preferably glass spheres. Preferably, moldings according to the invention have less than 3% by weight, preferably from 0.001 to 2% by mass and very particularly preferably from 0.05 to 1% by mass, of such auxiliaries, based on the sum of the components present. Likewise preferred according to the invention shaped bodies less than 75 mass%, preferably from 0.001 to 70 mass%, particularly preferably from 0.05 to 50 mass% and most preferably from 0.5 to 25 mass% of such fillers based on the Sum of existing components.
Anwendungsgebiete für diese Formkörper sind sowohl im Rapid Prototyping als auch im Rapid Manufacturing zu sehen. Mit Letzterem sind durchaus Kleinserien gemeint, also die Herstellung von mehr als einem gleichen Teil, bei dem aber die Produktion mittels eines Spritzgießwerkzeug nicht wirtschaftlich ist. Beispiele hierfür sind Teile für hochwertige PKW, die nur in kleinen Stückzahlen hergestellt werden, oder Ersatzteile für den Motorsport, bei denen neben den kleinen Stückzahlen auch der Zeitpunkt der Verfügbarkeit eine Rolle spielt. Branchen, in die die erfmdungsgemäßen Teile gehen, können beispielsweise die Luft- und Raumfahrtindustrie sein, die Medizintechnik, der Maschinenbau, der Automobilbau, die Sportindustrie, die Haushaltswarenindustrie, Elektroindustrie und Lifestyle.Fields of application for these moldings can be seen in both rapid prototyping and rapid manufacturing. With the latter are quite small series meant, so the production of more than one same part, but in which the production by means of an injection mold is not economical. Examples include parts for high-quality cars, which are only in small numbers or spare parts for motorsport, where in addition to the small quantities also the time of availability plays a role. Industries in which the inventive parts are concerned may be, for example, the aerospace industry, medical technology, mechanical engineering, automotive engineering, the sports industry, the household goods industry, the electrical industry and lifestyle.
Die in den nachfolgenden Beispielen durchgeführte Bestimmung der BET-Oberfläche erfolgte nach DIN 66 131. Die Schüttdichte wurde mit einer Apparatur gemäß DIN 53 466 ermittelt. Die Messwerte der Laserbeugung wurden an einem Malvern Mastersizer S, Ver. 2.18 erhalten.The determination of the BET surface area carried out in the following examples was carried out according to DIN 66 131. The bulk density was determined using an apparatus according to DIN 53 466. The laser diffraction measurements were taken on a Malvern Mastersizer S, Ver. 2.18 received.
Partikel aus PEEK mit einer BET-Oberfläche von 50 m2/g und einem mittleren Korndurchmesser von 500 µm wurden mit Hilfe einer cryogen arbeitenden Stiftmühle (Hosokawa Alpine CW 160) gemahlen. Dabei wurden die PEEK-Partikel über eine Förderschnecke in einen Mahlraum gefördert und währenddessen mit flüssigem Stickstoff auf -50 °C heruntergekühlt. In diesem Mahlraum wurden die PEEK-Partikel durch rotierende Stiftscheiben auf 220 m/s beschleunigt. Mit dieser Geschwindigkeit prallten sie auf die auf den Stiftscheiben angebrachten Stifte und wurden so einer starken Prallbeanspruchung ausgesetzt, die zum Bruch der Partikel führte. Dies geschah mit einem Durchsatz an PEEK-Partikeln von 15 kg/h. Den Mahlraum verließ ein micronisiertes Produkt mit einem Anteil von Partikeln kleiner als 100 µm von 30 Gew.-% (Siebanalyse mit Alpine Luftstrahlsieb nach DIN EN ISO 4610).Particles of PEEK with a BET surface area of 50 m 2 / g and a mean grain diameter of 500 μm were ground using a cryogenic pin mill (Hosokawa Alpine CW 160). The PEEK particles were conveyed via a screw conveyor into a grinding chamber and cooled down to -50 ° C with liquid nitrogen. In this grinding chamber, the PEEK particles were accelerated by rotating pin disks to 220 m / s. At this speed, they impacted the pins on the pin disks, exposing them to strong impact, causing the particles to break. This happened with a throughput of PEEK particles of 15 kg / h. The grinding chamber left a micronized product with a proportion of particles smaller than 100 microns of 30 wt .-% (sieve analysis with Alpine air jet sieve according to DIN EN ISO 4610).
Nach dem Micronisieren schloss sich der Prozessschnitt des Separierens an. Dabei wurden die zerkleinerten PEEK-Partikel mit Hilfe eines Alpine Luftstrahlsiebes mit nachgeschaltetem Zyklon fraktioniert. Die Fraktionierung erfolgte bei einer Maschenweite von 80 µm. Das so erhaltene Pulver war charakterisiert durch einen d10 von 16,7 µm, d50 von 52,6 µm und d90 von 113,8 µm.After micronization, the process cut of separation followed. The crushed PEEK particles were fractionated using an Alpine air jet screen with a downstream cyclone. The fractionation was carried out at a mesh size of 80 microns. The thus obtained Powder was characterized by a d 10 of 16.7 μm, d 50 of 52.6 μm and d 90 of 113.8 μm.
Zu 1900 g (100 Teile) PEEK-Pulver, hergestellt gemäß Beispiel 1, mit einem mittleren Korndurchmesser d50 von 52,6µm (Laserbeugung) wird 3,8 g Aerosil 200 (0,2 Teile) im Dry-Blend-Verfahren unter Benutzung eines Henschelmischers FML10/KM23 bei Raumtemperatur und 500 U/min in 3 Minuten untergemischt. An dem konfektionierten Pulver wurde eine Schüttdichte gemäß DIN 53 466 von 493 g/l gemessen. Die BET-Oberfläche beträgt 22,3 m2/g.To 1900 g (100 parts) of PEEK powder prepared according to Example 1, with a mean particle diameter d 50 of 52.6 microns (laser diffraction) is 3.8 g of Aerosil 200 (0.2 parts) using the dry-blend method using a Henschel mixer FML10 / KM23 at room temperature and 500 rev / min mixed in 3 minutes. On the ready-made powder, a bulk density according to DIN 53 466 of 493 g / l was measured. The BET surface area is 22.3 m 2 / g.
Zu 1900 g (100 Teile) PEEK-Pulver, hergestellt gemäß Beispiel 1, mit einem mittleren Korndurchmesser d50 von 52,6µm (Laserbeugung) wird 19 g (1 Teil) Iriodin® LS 825 im Dry-Blend-Verfahren unter Benutzung eines Henschelmischers FML10/KM23 bei 500 U/min bei 40 °C in 2 Minuten gemischt. Anschließend wurden 3,8 g Aerosil 200 (0,2 Teile) bei Raumtemperatur und 500 U/min in 3 Minuten untergemischt. An dem konfektionierten Pulver wurde eine Schüttdichte gemäß DIN 53 466 von 471 g/l gemessen. Die BET-Oberfläche beträgt 22,3 m2/g.To 1900 g (100 parts) of PEEK powder prepared according to Example 1, with a mean particle diameter d 50 of 52.6 microns (laser diffraction) is 19 g (1 part) Iriodin® LS 825 in a dry blend method using a Henschel mixer FML10 / KM23 mixed at 500 rpm at 40 ° C in 2 minutes. Subsequently, 3.8 g of Aerosil 200 (0.2 part) were mixed in at room temperature and 500 rpm for 3 minutes. On the prepared powder, a bulk density according to DIN 53 466 of 471 g / l was measured. The BET surface area is 22.3 m 2 / g.
Zu 1900 g (100 Teile) PEEK-Pulver, hergestellt gemäß Beispiel 1 mit einem mittleren Korndurchmesser d50 von 52,6 µm (Laserbeugung) wird 47 g (2,5 Teile) Printex alpha im Dry-Blend-Verfahren unter Benutzung eines Henschelmischers FML10/KM23 bei 700 U/min bei 50 °C in 2 Minuten gemischt. Anschließend wurden 1,0 g Aerosil R812 (0,05 Teile) bei Raumtemperatur und 500 U/min in 2 Minuten untergemischt. An dem konfektionierten Pulver wurde eine Schüttdichte gemäß DIN 53 466 von 450 g/l gemessen. Die BET-Oberfläche beträgt 22,3 m2/g.To 1900 g (100 parts) of PEEK powder, prepared according to Example 1 with a mean particle diameter d 50 of 52.6 microns (laser diffraction) is 47 g (2.5 parts) Printex alpha in a dry blend method using a Henschel mixer FML10 / KM23 mixed at 700 rpm at 50 ° C in 2 minutes. Subsequently, 1.0 g of Aerosil R812 (0.05 part) was mixed in at room temperature and 500 rpm in 2 minutes. On the prepared powder, a bulk density according to DIN 53 466 of 450 g / l was measured. The BET surface area is 22.3 m 2 / g.
Verkaufsprodukt von Victrex; das Granulat wurde auf einer Stiftrnühle der Firma Hosokawa Alpine CW 160 vermahlen. Die Temperatur betrug dabei -65 °C, trotzdem blieb die Ausbeute bei ca. 3 %. Die BET-Oberfläche des Ausgangsgranulates beträgt weniger als 0,1 m2/g.
Nach einer Schutzsiebung bei 120 µm wurden 2,0 g Aerosil 200 (0,1 Teile) bei Raumtemperatur und 500 U/min in 2 Minuten untergemischt. Der mittlere Korndurchmesser wurde mittels Laserbeugung mit 98 µm bestimmt. An dem konfektionierten Pulver wurde eine Schüttdichte gemäß DIN 53 466 von 499 g/l gemessen. Die BET-Oberfläche des Pulvers beträgt weniger als 0,1 g m2/g.Sales product of Victrex; The granules were ground on a pin mill from Hosokawa Alpine CW 160. The temperature was -65 ° C, yet the yield remained at about 3%. The BET surface area of the starting granules is less than 0.1 m 2 / g.
After a protective sieving at 120 μm, 2.0 g of Aerosil 200 (0.1 part) were mixed in at room temperature and 500 rpm in 2 minutes. The average grain diameter was determined by laser diffraction at 98 microns. On the prepared powder, a bulk density according to DIN 53 466 of 499 g / l was measured. The BET surface area of the powder is less than 0.1 gm 2 / g.
Ein 10x10 cm oben offener Kasten wurde mit einem Boden versehen, der über eine Spindel verfahrbar ist. Der Boden wurde bis auf einen halben Zentimeter an die obere Kante bewegt; der verbliebene Raum wurde mit Pulver gefüllt und mit einer Metallplatte glattgestrichen. Die Apparatur wurde in den Bauraum eines Nd:YAG-Lasers Star Mark 65 (Hersteller Carl Basel Lasertechnik) gestellt. Es wurde eine 4 mm breite und 20 mm lange Fläche durch den Laser aufgeschmolzen.
Die nächsten Schritte, Drehung der Spindel zum Absenken des Bodens um 0,15 mm sowie Auftrag der nächsten Pulverschicht, glattstreichen, und anschließend erneutes Belichten der 4 mm breiten und 20 mm langen Fläche durch den Nd:YAG-Laser zum Aufschmelzen des Pulvers, wurden einige Male wiederholt.A 10x10 cm open-top box was provided with a bottom, which is movable via a spindle. The floor was moved to half an inch to the top edge; the remaining space was filled with powder and smoothed with a metal plate. The apparatus was placed in the installation space of a Nd: YAG laser Star Mark 65 (manufacturer Carl Basel Laser Technology). A 4 mm wide and 20 mm long surface was melted by the laser.
The next steps, rotation of the spindle to lower the ground by 0.15 mm and application of the next powder layer, smooth down, and then re-exposing the 4 mm wide and 20 mm long surface by the Nd: YAG laser to melt the powder were repeated several times.
Das nicht mit Absorber versetzte Pulver aus den Beispielen 2 und 5 schmolz schlecht auf. Mit den Pulvern aus den Beispielen 3 und 4 konnten jedoch Plättchen mit der gewünschten Kontur hergestellt werden.
Besonders die Temperaturführung war jedoch noch zu optimieren, da durch das nicht automatisierte Handling und den Auftrag kalten Absorbers Curl auftrat.The non-absorber powder of Examples 2 and 5 melted poorly. With the powders of Examples 3 and 4, however, platelets could be made with the desired contour.
In particular, the temperature control was still to optimize, as occurred by the non-automated handling and the order of cold absorber Curl.
Die Pulver aus den Beispielen 2-5 wurden in der Lasersintermaschine des Herstellers EOS GmbH, Krailling, in Deutschland, getestet. Gearbeitet wurde mit der maximal möglichen Bauraumtemperatur von ca. 200 °C.
Das Pulver aus Beispiel 5 hatte kein Verarbeitungsfenster. Obwohl die maximal mögliche Energie eingebracht wurde, entstand kein glatter Schmelzefilm, sondern eine pickelige Oberfläche, auf der die einzelnen Körner noch zu erkennen waren. Eine zweite Schicht konnte nicht aufgetragen werden, da an den Kanten des Films starker Curl auftrat, das heißt ein Aufrollen der Kanten aus der Bauebene heraus. Bei Steigerung der Laserleistung in Richtung Maximalwert für den 50-Watt-Laser entstanden Aschepartikel, die sich auf der Bauplattform absetzten.
Das Pulver aus Beispiel 2 ließ sich verarbeiten, jedoch entstand ein Plättchen, welches relativ viele Lunker aufwies, was sich in der niedrigen Dichte niederschlug.
Die Pulver aus den Beispielen 3 und 4 ließen sich verarbeiten und erzeugten wesentlich dichtere Bauteile als das Pulver aus Beispiel 2.
The powder of Example 5 had no processing window. Although the maximum possible energy was introduced, there was no smooth melt film, but a spotty surface on which the individual grains were still visible. A second layer could not be applied because there was strong curl at the edges of the film, that is, curling up the edges out of the build plane. When the laser power was increased in the direction of the maximum value for the 50-watt laser, ash particles formed, which settled on the build platform.
The powder of Example 2 could be processed, however, a platelet was formed, which had relatively many voids, which was reflected in the low density.
The powders of Examples 3 and 4 could be processed and produced much denser components than the powder of Example 2.
Die Wärmeformbeständigkeiten der Bauteile aus den Beispielen 3 und 4 betrug nach DIN 53461, HDTB 218 bzw 221 °C. Ein lasergesintertes Bauteil aus dem Standardmaterial EOSINT P2200 GF hat eine Wärmeformbeständigkeit von 140 °C.The heat resistance of the components of Examples 3 and 4 was according to DIN 53461, HDTB 218 or 221 ° C. A laser-sintered component made of the standard material EOSINT P2200 GF has a heat resistance of 140 ° C.
Claims (42)
dadurch gekennzeichnet,
dass das Pulver Polyarylenetherketon aufweist und eine BET-Oberfläche zwischen 1 und 60 m2/g hat.Polymer powder for use in a layered process in which selectively areas of the respective powder layer are melted by the introduction of electromagnetic energy,
characterized,
that the powder comprises polyarylene ether ketone and has a BET surface area between 1 and 60 m 2 / g has.
dadurch gekennzeichnet,
dass das Pulver Polyarylenetherketon aufweist und eine BET-Oberfläche zwischen 5 und 45 m2/g hat.Polymer powder for use in a layered process in which selectively areas of the respective powder layer are melted by the introduction of electromagnetic energy,
characterized,
that the powder has polyarylene ether ketone and a BET surface area between 5 and 45 m 2 / g.
dadurch gekennzeichnet,
dass das Pulver Polyarylenetherketon aufweist und eine BET-Oberfläche zwischen 15 und 40 m2/g hat.Polymer powder for use in a layered process in which selectively areas of the respective powder layer are melted by the introduction of electromagnetic energy,
characterized,
that the powder comprises polyarylene ether ketone and has a BET surface between 15 and 40 m 2 / g has.
dadurch gekennzeichnet,
dass das Pulver zumindest ein Polymer aus der Gruppe Polyetheretherketon, Polyetherketon, Polyetherketonketon oder Polyetheretherketonketon aufweist.Polymer powder of at least one of claims 1 to 3,
characterized,
that the powder comprises at least one polymer selected from the group polyetheretherketone, polyether ketone, polyether ketone ketone, or polyether ether ketone ketone.
dadurch gekennzeichnet,
dass das Pulver einen mittleren Korndurchmesser zwischen 30 und 150 µm aufweist.Polymer powder according to at least one of claims 1 to 4,
characterized,
that the powder has a mean grain diameter between 30 and 150 microns.
dadurch gekennzeichnet,
dass das Pulver einen mittleren Korndurchmesser zwischen 45 und 120 µm aufweist.Polymer powder according to at least one of claims 1 to 5,
characterized,
that the powder has a mean grain diameter between 45 and 120 microns.
dadurch gekennzeichnet,
dass das Pulver einen mittleren Korndurchmesser zwischen 48 und 100 µm aufweist.Polymer powder according to at least one of claims 1 to 6,
characterized,
that the powder has a mean grain diameter between 48 and 100 microns.
dadurch gekennzeichnet,
dass das Pulver eine Lösungsviskosität in 96%iger Schwefelsäure nach EN ISO 1628-1 bzw. in Anlehnung an DIN EN ISO 307 zwischen 0,2 und 1,3 aufweist.Polymer powder according to at least one of claims 1 to 4,
characterized,
that the powder has a solution viscosity in 96% sulfuric acid according to EN ISO 1628-1 or, based on DIN EN ISO 307, between 0.2 and 1.3.
dadurch gekennzeichnet,
dass das Pulver eine Lösungsviskosität in 96%iger Schwefelsäure nach EN ISO 1628-1 bzw. in Anlehnung an DIN EN ISO 307 zwischen 0,5 und 1,1 aufweist.Polymer powder according to at least one of claims 1 to 4,
characterized,
that the powder has a solution viscosity in 96% sulfuric acid according to EN ISO 1628-1 or, based on DIN EN ISO 307, between 0.5 and 1.1.
dadurch gekennzeichnet,
dass ein Bauteil hergestellt nach einem erfindungsgemäßen Verfahren mit erfindungsgemäßem Pulver eine Lösungsviskosität in 96%iger Schwefelsäure nach EN ISO 1628-1 bzw. in Anlehnung an DIN EN ISO 307 aufweist, die höher oder gleich ist wie die Lösungsviskosität des verwendeten Pulvers.Polymer powder according to at least one of claims 1 to 4,
characterized,
that a component produced by a process according to the invention with inventive powder has a solution viscosity in 96% sulfuric acid according to EN ISO 1628-1 or based on DIN EN ISO 307, which is higher than or equal to the solution viscosity of the powder used.
dadurch gekennzeichnet,
dass es zusätzlich zumindest einen Hilfsstoff und/oder zumindest einen Füllstoff und/oder zumindest ein Pigment und/oder zumindest einen Absorber aufweist.Powder according to at least one of claims 1 to 10,
characterized,
in that it additionally has at least one adjuvant and / or at least one filler and / or at least one pigment and / or at least one absorber.
dadurch gekennzeichnet,
dass es als Hilfsstoff Rieselhilfsmittel aufweist.Powder according to claim 11,
characterized,
that it has flow aids as adjuvant.
dadurch gekennzeichnet,
dass der Absorber Farbmittel aufweist.Powder according to at least one of claims 1 to 12,
characterized,
that the absorber has colorant.
dadurch gekennzeichnet,
dass der Absorber Farbstoffe aufweist.Powder according to claim 13,
characterized,
that the absorber comprises dyes.
dadurch gekennzeichnet,
dass der Absorber Pigmente aufweist.Powder according to claim 13,
characterized,
that the absorber has pigments.
dadurch gekennzeichnet,
dass der Absorber Ruß, KHP, Knochenkohle, Graphit, Kohlenstofffasern, Kreide oder Interferenzpigmente aufweist.Powder according to one of claims 1 to 15,
characterized,
that comprises the absorber carbon black, KHP, bone charcoal, graphite, carbon fibers, chalk, or interference pigments.
dadurch gekennzeichnet,
dass der Absorber neben Ruß, KHP, Knochenkohle, Graphit, Kohlenstofffasern, Kreide oder Interferenzpigmenten weitere Komponenten aufweist.Powder according to one of claims 1 to 16
characterized,
that the absorber in addition to carbon black, KHP, bone char, graphite, carbon fibers, chalk or interference pigments has other components.
dadurch gekennzeichnet,
dass der Absorber Flammschutzmittel basierend auf Phosphor oder Melamincyanurat aufweist.Powder according to one of claims 1 to 17,
characterized,
comprises based on phosphorus or melamine cyanurate that the absorber flame retardants.
dadurch gekennzeichnet,
dass das Pulver die Absorberkomponente pulverförmig mit einer mittleren Partikelgröße von 0,001 bis 50 µm aufweist.Powder according to one of claims 1 to 18,
characterized,
that the powder comprises the absorber component in powder form with an average particle size of 0.001 to 50 microns.
dadurch gekennzeichnet,
dass das Pulver bezogen auf die Summe der im Pulver vorhandenen Polymere von 0,01 bis 30 Gew.-% Absorber aufweist.Polymer powder according to at least one of claims 1 to 19,
characterized,
that the powder based on the sum of the polymers present in the powder from 0.01 to 30 wt .-% absorber.
dadurch gekennzeichnet,
dass das Pulver bezogen auf die Summe der im Pulver vorhandenen Polymere von 0,05 bis 20 Gew.-% Absorber aufweist.Polymer powder according to claim 20,
characterized,
that the powder based on the sum of the polymers present in the powder from 0.05 to 20 wt .-% absorber.
dadurch gekennzeichnet,
dass das Pulver bezogen auf die Summe der im Pulver vorhandenen Polymere von 0,2 bis 15 Gew.-% Absorber aufweist.Polymer powder according to claim 21,
characterized,
that the powder based on the sum of the polymers present in the powder from 0.2 to 15 wt .-% absorber.
dadurch gekennzeichnet,
dass das Pulver bezogen auf die Summe der im Pulver vorhandenen Polymere von 0,4 bis 10 Gew.-% Absorber aufweist.Polymer powder according to claim 22,
characterized,
that the powder based on the sum of the polymers present in the powder from 0.4 to 10 wt .-% absorber.
dadurch gekennzeichnet,
dass das Pulver eine Mischung von Rußpartikeln und Polymerpartikeln aufweist.Polymer powder according to at least one of claims 1 to 23,
characterized,
that the powder has a mixture of soot particles and polymer particles.
dadurch gekennzeichnet,
dass die Rußpartikel hydrophilisiert sind.Polymer powder according to at least one of claims 1 to 24,
characterized,
that the soot particles are hydrophilized.
dadurch gekennzeichnet,
dass die Rußpartikel hydrophobisiert sind.Polymer powder according to at least one of claims 1 to 24,
characterized,
that the soot particles are hydrophobized.
dadurch gekennzeichnet,
dass es als Füllstoff Glaspartikel und/oder Alugrieß aufweist.Polymer powder according to claim 11,
characterized,
that it has as a filler glass particles and / or Alugrieß.
dadurch gekennzeichnet,
dass zumindest ein Polymerpulver mit Absorber vermischt wird.Process for the preparation of polymer powder according to at least one of Claims 1 to 27,
characterized,
that at least one polymer powder is mixed with absorber.
dadurch gekennzeichnet,
dass er ein Polymer aus der Gruppe Polyarylenetherketon aufweist.Shaped body produced by one of the methods of claims 29 to 33
characterized,
that it comprises a polymer from the group polyarylene ether ketone.
dadurch gekennzeichnet,
dass er zumindest ein Polymer aus der Gruppe Polyetheretherketon, Polyetherketon, Polyetherketonketon oder Polyetheretherketonketon aufweist.Shaped body produced by one of the methods of claims 29 to 33
characterized,
that it comprises at least one polymer from the group polyetheretherketone, polyetherketone, polyetherketone ketone or polyetheretherketone ketone.
dadurch gekennzeichnet,
dass er bezogen auf die Summe der vorhandenen Polymere von 0,01 bis 30 Gew.-% Absorber aufweist.Shaped body according to claim 34 or 35,
characterized,
that it has based on the sum of the existing polymers from 0.01 to 30 wt .-% absorber.
dadurch gekennzeichnet,
dass er Farbmittel aufweist.Shaped body according to at least one of claims 34 to 36,
characterized,
that he has colorant.
dadurch gekennzeichnet,
dass er Farbstoffe aufweist.Shaped body according to claim 37,
characterized,
that he has dyes.
dadurch gekennzeichnet,
dass er Pigmente aufweist.Shaped body according to claim 37,
characterized,
that he has pigments.
dadurch gekennzeichnet,
dass er Ruß, KHP, Knochenkohle, Graphit, Kohlenstofffasern, Kreide oder Interferenzpigmente oder Flammschutzmittel basierend auf Phosphor oder auf Melamincyanurat aufweist.Shaped body according to at least one of claims 35 to 39,
characterized,
that it comprises carbon black, KHP, bone char, graphite, carbon fibers, chalk or interference pigments or flame retardants based on phosphorus or on melamine cyanurate.
dadurch gekennzeichnet,
dass er Füllstoffe und/oder Hilfsstoffe aufweist.Shaped body according to at least one of claims 34 to 40,
characterized,
that it has fillers and / or auxiliaries.
dadurch gekennzeichnet,
dass er Verwendung in zumindest einem der Anwendungsgebiete der Luft- und Raumfahrtindustrie, im Automobilbau, im Maschinenbau, in der Medizintechnik, in der Sportindustrie, in der Elektronikindustrie, in der Haushaltswarenindustrie oder im Bereich Lifestyle findet.Shaped body according to at least one of claims 34 to 41,
characterized,
that it finds use in at least one of the aerospace, automotive, engineering, medical, sports, electronics, household goods, and lifestyle industries.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL05110112T PL1674497T3 (en) | 2004-12-21 | 2005-10-28 | Use of polyarylene ether ketone powder in a powder-based tridimensional tool-less method of manufacturing and shaped articles obtained therefrom |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102004062761A DE102004062761A1 (en) | 2004-12-21 | 2004-12-21 | Use of polyarylene ether ketone powder in a three-dimensional powder-based tool-less production process, and moldings produced therefrom |
Publications (2)
Publication Number | Publication Date |
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EP1674497A1 true EP1674497A1 (en) | 2006-06-28 |
EP1674497B1 EP1674497B1 (en) | 2008-08-13 |
Family
ID=35929583
Family Applications (1)
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EP05110112A Revoked EP1674497B1 (en) | 2004-12-21 | 2005-10-28 | Use of polyarylene ether ketone powder in a powder-based tridimensional tool-less method of manufacturing and shaped articles obtained therefrom |
Country Status (14)
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US (1) | US20060134419A1 (en) |
EP (1) | EP1674497B1 (en) |
JP (1) | JP5156189B2 (en) |
KR (1) | KR20060071340A (en) |
CN (1) | CN1827689B (en) |
AT (1) | ATE404608T1 (en) |
AU (1) | AU2005246985A1 (en) |
CA (1) | CA2530762A1 (en) |
DE (2) | DE102004062761A1 (en) |
ES (1) | ES2311932T3 (en) |
NO (1) | NO20056075L (en) |
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PL (1) | PL1674497T3 (en) |
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Also Published As
Publication number | Publication date |
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US20060134419A1 (en) | 2006-06-22 |
ATE404608T1 (en) | 2008-08-15 |
CN1827689B (en) | 2014-08-20 |
NZ544275A (en) | 2007-09-28 |
DE502005005017D1 (en) | 2008-09-25 |
ES2311932T3 (en) | 2009-02-16 |
KR20060071340A (en) | 2006-06-26 |
CN1827689A (en) | 2006-09-06 |
PL1674497T3 (en) | 2009-01-30 |
AU2005246985A1 (en) | 2006-07-06 |
TW200634093A (en) | 2006-10-01 |
DE102004062761A1 (en) | 2006-06-22 |
EP1674497B1 (en) | 2008-08-13 |
JP2007039631A (en) | 2007-02-15 |
JP5156189B2 (en) | 2013-03-06 |
CA2530762A1 (en) | 2006-06-21 |
NO20056075L (en) | 2006-06-22 |
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